Are songbirds at risk from lead at small arms ranges? An application of the spatially explicit exposure model.

Use of small arms during training is an important activity associated with the development and proficiency of soldiers. These weapons traditionally have used copper-jacketed lead projectiles; the copper facilitates the oxidation of the metallic lead resulting in more mobile oxides and carbonates. Consequently, many ranges at installations have high soil concentrations of lead. Many of these ranges are no longer used and have become habitat for wildlife. To address the potential for adverse effects from lead exposure in songbirds, we compared the outputs of traditional deterministic exposure models with a spatial model and compared the results of both with blood-lead levels from songbird species at two small arms range complexes. An integrative data collection procedure was used and incorporated into the spatially explicit exposure model (SEEM) for two small arms range sites. Site-specific data were used to refine model input parameters. These data included lead soil concentrations, analysis of lead concentrations in nestling food items, acid-insoluble ash content of feces (to estimate soil ingestion), location and mapping of singing males, and nest site location and characteristics. Territorial males also were spot-mapped to determine likelihood of breeding activity. Modeled estimates of risk were compared with blood and feather lead levels of adults and nestlings. Overall, edge species had higher blood-lead concentrations; however, most had concentrations below subclinical effect levels. Conventional deterministic methods produced risk estimates exceeding 10-fold the highest SEEM estimates. The spatially explicit exposure model provided good agreement with field observations and therefore produced more accurate risk estimates. The present study provides support for the application of spatial methods over conventional deterministic methods.

Tetrathiolate coordination of germanium(IV) in a protein active site.

The tetracysteine metal coordination site of the rubredoxins from Clostridium pasteurianum (Cp) and Pyrococcus furiosus (Pf) are shown to stably bind the inorganic Ge(IV) ion. This is the first characterized coordination complex of tetravalent germanium with a biological macromolecule. Zn(II), Ga(III) and Ge(IV) substitution yields differential NMR chemical shifts for the 1H and 15N amide resonances throughout much of the protein structure. The differential shifts for the six backbone amides that hydrogen bond to the metal-coordinated sulfurs indicate that the pseudo 2-fold symmetry of the active site is more closely maintained in the hyperthermophile Pf rubredoxin than in its mesophile Cp homolog. These three metal substitutions form an isoelectronic series of small diamagnetic proteins for which reference structures are known to 1A resolution. These series provide a promising system to analyze theoretical predictions of the effects of differential charge distribution on chemical shifts from both proximal and long range interactions.