Atmospheric mercury emissions and speciation at the sulphur bank mercury mine superfund site, Northern California

One pathway for release of mercury (Hg) from naturally enriched sites is emission to the atmosphere. Elemental Hg, when emitted, will enter the global atmospheric pool. In contrast, if reactive gaseous Hg or Hg2+ (as HgCl2, HgBr2, or HgOH2) is formed, it will most likely be deposited locally. This study focused on the measurement of elemental Hg flux and reactive gaseous Hg concentrations at the Sulphur Bank Superfund Site, an area of natural Hg enrichment with anthropogenic disturbance and ongoing geothermal activity. Mean Hg emissions ranged from 14 to 11000 ng m(-2) h(-1), with the highest emissions from anthropogenically disturbed materials. Reactive gaseous Hg concentrations were the highest ever reported for a natural setting (0.3-76 ng m(-3)). Measured Hg fluxes were used within a Geographic Information System to estimate mercury releases to the atmosphere from the site. Results indicated approximately 17 kg of Hg y(-1) of is emitted to the atmosphere from the 3.8 km2 area, with half from mine waste, ore, and tailing piles and half from relatively undisturbed naturally enriched substrate.     

Free radical destruction of N-nitrosodimethylamine in water

Absolute rate constants for the reactions of the hydroxyl radical, hydrated electron, and hydrogen atom with N-nitrosodimethylamine (NDMA) in water at room temperature have been determined using electron pulse radiolysis and transient absorption spectroscopy (*OH and e- aq) and EPR free induction decay attenuation (*H) measurements. Specific values of (4.30 +/- 0.12) x 10(8), (1.41 +/- 0.02) x 10(10), and (2.01 +/- 0.03) x 10(8) M(-1) s(-1) were measured, respectively. DMPO spin-trapping experiments demonstrated that the hydroxyl radical reaction with NDMA occurs by hydrogen atom abstraction from a methyl group, and the rate constant for the subsequent reaction of this radical transient with dissolved oxygen was measured as (5.3 +/- 0.6) x 10(6) M(-1) s(-1). This relatively slow rate constant implies that regeneration of the parent nitrosoamine from the oxidized transient could occur in natural waters containing dissolved organic compounds. The reaction of the hydrated electron with NDMA was to form a transient adduct anion, which could subsequently transfer this excess electron to regenerate the parent chemical. Such regeneration reactions would significantly reduce the effectiveness of any applied advanced oxidation technology remediation effort on NDMA-contaminated natural waters.     

Inhibition of pyrite oxidation by a phospholipid in the presence of silicate

The influence of sodium silicate on the ability of a diacetylene-containing phospholipid (23:2 diyne PC) to inhibit the oxidation of pyrite at pH 2 and pH 6 was investigated. The phospholipid used has previously been reported to show up to 80% suppression of pyrite oxidation and to show excellent stability down to at least pH 2. Pyrite was leached with a solution containing Fe3+ but no coating agent and three different solutions or treatments: a lipid treatment, a silicate treatment, and a lipid + silicate treatment. Pyrite oxidation was based on iron (Fe3+, Fe2+) leached out of a continuous-flow porous-bed reactor system. The results show that at pH 6 the silicate and lipid both bind strongly to the pyrite surfaces, providing a barrier that inhibits the production and subsequent release of oxidation products. The lipid is superior to the silicate in suppressing pyrite oxidation at both pH 2 and pH 6. Also, the presence of silicates decreased the ability for the lipid to suppress pyrite oxidation, both at pH 2 and pH 6. The reaction mechanism for pyrite oxidation at pH 2 is first order for pyrite leached by solutions containing only ferric, ferric together with silicate, and ferric combined with silicate and lipid. The only treatment that effectively prevented pyrite oxidation at pH 2 was the lipid treatment. The Fe speciation results are supported by both SEM images and EDS calculations.     

Assessing blood flow control through a bootstrap method

In order to assess blood flow control, the relationship between blood pressure and blood flow can be modeled by linear filters. We present a bootstrap method, which allows the statistical analysis of an index of blood flow control that is obtained from constrained system identification using an established set of pre-defined filters.     

Chronic measurement of the stimulation selectivity of the flat interface nerve electrode

The flat interface nerve electrode (FINE) is an attempt to improve the stimulation selectivity of extraneural electrodes. By reshaping peripheral nerves into elliptical cylinders, central fibers are moved closer to the nerve-electrode interface, and additional surface area is created for contact placement. The goals of this study were to test the hypothesis that greater nerve reshaping leads to improved selectivity and to examine the chronic recruitment properties of the FINE. Three FINEs were developed to reshape peripheral nerves to different degrees. Four electrodes of each type were implanted on the sciatic nerves of 12 cats and tested for selectivity over at least three months. There was physiologic evidence of nerve injury in two cats with the tightest cuffs, but the other animals behaved normally. All cuff types were capable of selectively activating branches of the sciatic nerve, as well as groups of fibers within branches. The electrodes that moderately reshaped the nerves demonstrated the most selectivity. Both the selectivity measurements and the recruitment curve characteristics were stable throughout the implant period. From an electrophysiological standpoint, the FINE is a viable alternative for neuroprosthetic devices. A histological analysis of the nerves is under way to evaluate the safety of the FINE.     

Characterization of the binding site for inhibitors of the HPV11 E1-E2 protein interaction on the E2 transactivation domain by photoaffinity labeling and mass spectrometry

An indandione-containing class of inhibitors abrogates DNA replication of human papillomavirus (HPV) types 6 and 11 by binding reversibly to the transactivation domain (TAD) of the viral E2 protein and inhibiting its interaction with the viral E1 helicase. To locate the binding site of this class of protein-protein interaction inhibitors, a benzophenone derivative was used to generate an irreversibly labeled E2-TAD polypeptide. The single site of covalent modification of the E2-TAD was identified by proteolytic digestions using trypsin, LysC, and V8 proteases and characterization of the resulting peptides by LC-MS procedures. Through this methodology, the benzophenone attachment point was located at the terminal methyl of residue Met101. Evidence further pinpointed the site of photoaffinity attachment to the terminal carbon atom, which is significant in providing a definitive example of the ability to locate photoinduced cross-linking to a polypeptide with atomic resolution using solely mass spectrometric detection. The location of the inhibitor binding site vis-à-vis the Glu39 and Glu100 residues sensitive to mutation for HPV 11 E2-TAD is discussed in relation to the crystal structure of the E2-TAD from the related HPV type 16.     

Deformation-induced release of ATP from erythrocytes in a poly(dimethylsiloxane)-based microchip with channels that mimic resistance vessels

The ability of nitric oxide to relax smooth muscle cells surrounding resistance vessels in vivo is well documented. Here, we describe a series of studies designed to quantify amounts of adenosine triphosphate (ATP), a known stimulus of NO production in endothelial cells, released from erythrocytes that are mechanically deformed as these cells traverse microbore channels in lithographically patterned microchips. Results indicate that micromolar amounts of ATP are released from erythrocytes flowing through channels having cross sectional dimensions of 60 x 38 micron (2.22 +/- 0.50 microM ATP). Microscopic images indicate that erythrocytes, when being pumped through the microchip channels, migrate toward the center of the channels, leaving a cell-free or skimming layer at the walls of the channel, a profile known to exist in circulatory vessels in vivo. A comparison of the amounts of ATP released from RBCs mechanically deformed in microbore tubing (2.54 +/- 0.15 microM) vs a microchip (2.59 +/- 0.32 microM) suggests that channels in microchips may serve as functional biomimics of the microvasculature. Control studies involving diamide, a membrane-stiffening agent, suggest that the RBC-derived ATP is not due to cell lysis but rather physical deformation.     

Effects of nonlinearities and uncorrelated or correlated errors in realistic simulated data on the prediction abilities of augmented classical least squares and partial least squares

Comparisons of prediction models from the new augmented classical least squares (ACLS) and partial least squares (PLS) multivariate spectral analysis methods were conducted using simulated data containing deviations from the idealized model. The simulated data were based on pure spectral components derived from real near-infrared spectra of multicomponent dilute aqueous solutions. Simulated uncorrelated concentration errors, uncorrelated and correlated spectral noise, and nonlinear spectral responses were included to evaluate the methods on situations representative of experimental data. The statistical significance of differences in prediction ability was evaluated using the Wilcoxon signed rank test. The prediction differences were found to be dependent on the type of noise added, the numbers of calibration samples, and the component being predicted. For analyses applied to simulated spectra with noise-free nonlinear response, PLS was shown to be statistically superior to ACLS for most of the cases. With added uncorrelated spectral noise, both methods performed comparably. Using 50 calibration samples with simulated correlated spectral noise, PLS showed an advantage in 3 out of 9 cases, but the advantage dropped to 1 out of 9 cases with 25 calibration samples. For cases with different noise distributions between calibration and validation, ACLS predictions were statistically better than PLS for two of the four components. Also, when experimentally derived correlated spectral error was added, ACLS gave better predictions that were statistically significant in 15 out of 24 cases simulated. On data sets with nonuniform noise, neither method was statistically better, although ACLS usually had smaller standard errors of prediction (SEPs). The varying results emphasize the need to use realistic simulations when making comparisons between various multivariate calibration methods. Even when the differences between the standard error of predictions were statistically significant, in most cases the differences in SEP were small. This study demonstrated that unlike CLS, ACLS is competitive with PLS in modeling nonlinearities in spectra without knowledge of all the component concentrations. This competitiveness is important when maintaining and transferring models for system drift, spectrometer differences, and unmodeled components, since ACLS models can be rapidly updated during prediction when used in conjunction with the prediction augmented classical least squares (PACLS) method, while PLS requires full recalibration.     

A non-lensed fiber-optic resonance-enhanced multiphoton ionization probe

We have developed a miniature fiber-optic probe with no focusing optics for in situ analysis of volatile organic compounds (VOCs). The probe uses an optical fiber to transmit a laser pulse to a vapor sample causing it to ionize adjacent to the fiber tip through a resonance-enhanced multiphoton ionization (REMPI) process. The distal end of the optical fiber is contained co-axially within 2-mm-inner-diameter stainless steel tubing that serves as an electrode. The electrode is biased at a high positive potential to collect electrons. The current generated is shown to be proportional over about two orders of magnitude to the concentration of the species ionized. Visible wavelength REMPI spectroscopy is used to determine probe sensitivities of 20 ppb (benzene) and 43 ppb (toluene). Designing the probe without focusing optics specifies an achromatic ionization region constant in size and position as the laser wavelength is scanned, which simplifies data collection and reduction. Focusing achromatic systems are discussed and the potential signal improvement is estimated.     

Radionuclide biokinetics database (RBDATA-EULEP): an update

The main activity of the RBDATA-EULEP project is the development of an electronic database of information on the biokinetics of radionuclides after intake by inhalation, ingestion or injection. It consists of linked tables of publications and experiments, with details and comments on the materials, procedures and results. By March 2004 it contained information on more than 1600 experiments from 600 publications. It will be extended and Internet access will also be provided.