Femtosecond real-time probing of reactions. IV. The reactions of alkali halides

The photodissociation dynamics of some alkali halides are explored via the method of femtosecond transition-state spectroscopy (FTS). The alkali halide dissociation reaction is influenced by the interaction between the covalent and the ground state ionic potential energy surfaces (PES), which cross at a certain internuclear separation. Depending upon the adiabaticity of the PES, the dissociating fragments may be trapped in a well formed by the avoided crossing of these surfaces. Here, we detail the FTS results of this class of reactions, with particular focus on the reaction of sodium iodide: NaI*-->[Na---I]°* -->Na+I. As in our first report [T. S. Rose, M. J. Rosker, and A. H. Zewail, J. Chem. Phys. 88, 6672 (1988)], we observe the dynamical motion of the wave packet along the reaction coordinate and the crossing between the covalent and ionic surfaces. The studies presented here characterize the effects of various experimental parameters, including pump and probe wavelengths, on the dynamics of the dissociation and its detection. Comparisons of the results with classical and quantum mechanical calculations are also presented

A Case Study of Tire Crumb Use on Playgrounds: Risk Analysis and Communication When Major Clinical Knowledge Gaps Exist

Physicians and public health professionals working with the U.S. Environmental Protection Agency’s Region 8 Pediatric Environmental Health Specialty Unit (PEHSU) received several telephone calls requesting information regarding the safety of recycled tire crumb as a playground surface constituent placed below children’s play structures. There were no reported symptoms or adverse health effects in exposed children. The literature available on the safety and risk of exposure to crumb rubber constituents was limited and revealed no information quantifying exposures associated with product use. Callers were informed by the PEHSU that no evidence existed suggesting harm from intended use of the product, but gaps in knowledge about the product were identified and communicated. Here the case of crumb rubber on playgrounds is used as a model to present an approach to similar environmental medicine questions. From defining the question, to surveying traditional and nontraditional resources for information, synthesis of findings, and risk communication, the case provides a model to approach similar questions

Recruitment in Degraded Marine Habitats: A Spatially Explicit, Individual-Based Model for Spiny Lobster

Coastal habitats that serve as nursery grounds for numerous marine species are badly degraded, yet the traditional means of modeling populations of exploited marine species handle spatiotemporal changes in habitat characteristics and life history dynamics poorly, if at all. To explore how nursery habitat degradation impacts recruitment of a mobile, benthic species, we developed a spatially explicit, individual-based model that describes the recruitment of Caribbean spiny lobster (Panulirus argus) in the Florida Keys, where a cascade of environmental disturbances has reconfigured nursery habitat structure. In recent years, the region has experienced a series of linked perturbations, among them, seagrass die-offs, cyanobacteria blooms, and the mass mortality of sponges. Sponges are important shelters for juvenile spiny lobster, an abundant benthic predator that also sustains Florida\u27s most valuable fishery. In the model, we simulated monthly settlement of individual lobster postlarvae and the daily growth, mortality, shelter selection, and movement of individual juvenile lobsters on a spatially explicit grid of habitat cells configured to represent the Florida Keys coastal nursery. Based on field habitat surveys, cells were designated as either seagrass or hard-bottom, and hard-bottom cells were further characterized in terms of their shelter- and size-specific lobster carrying capacities. The effect of algal blooms on sponge mortality, hence lobster habitat structure, was modeled based on the duration of exposure of each habitat cell to the blooms. Ten-year simulations of lobster recruitment with and without algal blooms suggest that the lobster population should be surprisingly resilient to massive disturbances of this type. Data not used in model development showed that predictions of large changes in lobster shelter utilization, yet small effects on recruitment in response to blooms, were realistic. The potentially severe impacts of habitat loss on recruitment were averted by compensatory changes in habitat utilization and mobility by larger individuals, coupled with periods of fortuitously high larval settlement. Our model provides an underutilized approach for assessing habitat effects on open populations with complex life histories, and our results illustrate the potential pitfalls of relying on intuition to infer the effects of habitat perturbations on upper trophic levels

Demographic Responses of Least Terns and Piping Plovers to the 2011 Missouri River Flood—A Large-Scale Case Study

2011 led to substantial changes in abundance and distribution of unvegetated sand habitat. This river system is a major component of the breeding range for interior Least terns (Sternula antillarum; “terns”) and piping plovers (Charadrius melodus; “plovers”), both of which are Federally listed ground-nesting birds that prefer open, unvegetated sand and gravel nesting substrates on sandbars and shorelines. The 2011 flood inundated essentially all tern and plover nesting habitat during 2011, but it had potential to generate post-flood habitat conditions that favored use by terns and plovers in subsequent years. We compared several tern and plover demographic parameters during the pre-flood and post-flood periods on the Garrison Reach and Lake Sakakawea, North Dakota, to determine how this event influenced these species (both species on the Garrison Reach, and plovers only on Lake Sakakawea). The principal parameters we measured (nest survival, chick survival, and breeding population) showed spatial and temporal variation typical of opportunistic species occupying highly variable habitats. There was little evidence that nest survival of least terns differed between pre- and post-flood. During 2012 when habitat was most abundant on the Garrison Reach and Lake Sakakawea, piping plover nest survival was higher than in any other year in the study, but returned to rates comparable to pre-flood years in 2013. Chick survival for terns on the Garrison Reach and plovers on Lake Sakakawea showed a similar pattern to plover nest survival, with the 2012 rate exceeding all other years of the study, and the remaining pre-flood and post-flood years being generally similar but slightly higher in post-flood years. However, plover chick survival on the Garrison Reach in 2012 was similar to pre-flood years, and increased annually thereafter to its highest rate in 2014. Although wide confidence intervals precluded firm conclusions about flood effects on breeding populations, the general pattern suggested lower populations of plovers but higher populations of least terns immediately after the flood. Despite near total absence of breeding habitat on either study area during the flood of 2011, populations of both species persisted after the flood due to their propensity to disperse and/or forgo breeding for at least a year. Tern and plover populations have similarly persisted and recovered after the flood, but their mechanisms for persistence likely differ. Data on tern dispersal is generally lacking, but they are thought to show little fidelity to their natal grounds, have a propensity to disperse potentially long distances, and routinely forgo breeding until their second year, thus a lost opportunity to breed in a given area may be easily overcome. Plovers exhibit stronger demographic ties to the general area in which they previously nested, yet they occupy much broader nesting habitat features than terns and exploit three major landforms in the Dakotas (free-flowing rivers, reservoir shorelines, and wetland shorelines). Consequently, dispersal to and from non-Missouri River habitats and potential to exploit non-traditional habitats likely sustained the Northern Great Plains population through the flood event. Terns and plovers normally occupy similar habitats on the Missouri River and both species experienced similar loss of a breeding season due to the flood. Persistence of these populations after the flood underscores the importance of understanding their unique demographic characteristics and the context within which the Missouri River operates

Sulfur dioxide and particles in quiescent volcanic plumes from Poás, Arenal, and Colima Volcanos, Costa Rica and Mexico

Measurements of SO2 emission rates and concentrations and of particle distribution, size, shape, and composition were made in quiescent volcanic plumes emitted into the troposphere from Poás and Arenal volcanos, Costa Rica, and Colima volcano, Mexico. SO2 emission rates were 700±180 metric tons per day (t/d) for Poás, 210±30 t/d for Arenal, and 320±50 t/d for Colima. The concentrations of SO2 calculated from the COSPEC/lidar data were 5–380 ppb. Concentrations of SO2measured directly by flame photometry were 10–250 ppb. Particles collected in the plumes with a quartz crystal microbalance impactor were mostly less than 3 μm in diameter and consisted of droplets of dilute sulfur-bearing solutions and minor amounts of larger silicate particles coated with a sulfur-bearing film or crust. Total particle concentrations were 4.7 μg/m3 for Poás and 18.8 μg/m3for Colima. Comparison of concentrations of SO2 in the plumes with gas samples collected at fumaroles on the ground suggests that the plumes are diluted by the atmosphere by factors of up to 105