Synthesis and characterization of polyethylene-like polyurethanes derived from long-chain, aliphatic α,ω-diols

Long-chain aliphatic α,ω-diols containing up to 32 consecutive methylene groups were synthesized by several methods and characterized. 1,22-Docosanediol HO-(CH₂)₂₂-OH and 1,32-dotriacontanediol HO-(CH₂)₃₂-OH both exhibited a solid-solid phase transition before melting. The α,ω-diols HO-(CH₂)_m-OH, where m=12, 22, or 32, were reacted in the melt with much shorter aliphatic α,ω-diisocyanates OCN-(CH₂)_n-NCO, where n=4, 6, 8, or 12, producing a series of linear, aliphatic, and increasingly polyethylene-like m,n-polyurethanes. Characterization (by DSC, TGA, and SAXS) of the m,n-polyurethane series showed that when the aliphatic segments were increased, and the hydrogen-bonding densities thus decreased, the polymers displayed physical and thermal properties (for example, solubility and melting temperature) typical of polyethylene.     

Polymer electrolyte membranes from fluorinated polyisoprene-block-sulfonated polystyrene: Structural evolution with hydration and heating

Small-angle neutron scattering (SANS) and ultra-small-angle X-ray scattering (USAXS) have been used to study the structural changes in fluorinated polyisoprene/sulfonated polystyrene (FISS) diblock copolymers as they evolved from the dry state to the water swollen state. A dilation of the nanometer-scale hydrophilic domains has been observed as hydration increased, with greater dilation occurring in the more highly sulfonated samples or upon hydration at higher temperatures. Furthermore, a decrease in the order in these phase separated structures is observed upon swelling. The glass transition temperatures of the fluorinated blocks have been observed to decrease upon hydration of these materials, and at the highest hydration levels, differential scanning calorimetry (DSC) has shown the presence of tightly bound water. A precipitous drop in the mechanical integrity of the 50% sulfonated materials is also observed upon exceeding the glass transition temperature (T_g), as measured by dynamic mechanical analysis (DMA).     

Waterfall formation at a desert river–reservoir delta isolates endangered fishes

Unforeseen interactions of dams and declining water availability have formed new obstacles to recovering endemic and endangered big‐river fishes. During a recent trend of drying climate and declining reservoir water levels in the Southwestern United States, a large waterfall has formed on two separate occasions (1989–1995 and 2001–present) in the transition zone between the San Juan River and Lake Powell reservoir because of deposited sediments. Since recovery plans for two large‐bodied endangered fish species, razorback sucker (Xyrauchen texanus) and Colorado pikeminnow (Ptychocheilus lucius), include annual stockings in the San Juan River, this waterfall potentially blocks upstream movement of individuals that moved downstream from the river into the reservoir. To quantify the temporal variation in abundance of endangered fishes aggregating downstream of the waterfall and determine population demographics, we remotely monitored and sampled in spring 2015, 2016, and 2017 when these fish were thought to move upstream to spawn. Additionally, we used an open population model applied to tagged fish detected in 2017 to estimate population sizes. Colorado pikeminnow were so infrequently encountered (<30 individuals) that population estimates were not performed. Razorback sucker captures from sampling (335), and detections from remote monitoring (943) showed high abundance across all 3 years. The razorback sucker population estimate for 2017 alone was 755 individuals and, relative to recent population estimates ranging from ~2,000 to ~4,000 individuals, suggests that a substantial population exists seasonally downstream of this barrier. Barriers to fish movement in rivers above reservoirs are not unique; thus, the formation of this waterfall exemplifies how water development and hydrology can interact to cause unforeseen changes to a riverscape.     

Efficacy of Mechanically Removing Nonnative Predators from a Desert Stream

Native fish faunas throughout the American Southwest have declined dramatically in the past century, mainly a consequence of habitat alteration and alien species introductions. We initiated this 6‐year study to evaluate the efficacy of mechanical removal of nonnative predaceous rainbow trout Oncorhynchus mykiss, brown trout Salmo trutta, yellow bullhead Ameiurus natalis and smallmouth bass Micropterus dolomieu from an open 4.6‐km reach of West Fork Gila River in southwest New Mexico, USA. Removal efforts involved intensive sampling with a 10‐ to 12‐person crew using backpack electrofishers and seines to capture fish over a 4‐ to 5‐day period each year. Additionally, two reference sites were sampled with similar methods to compare temporal changes in species mass in the absence of a removal effort. Results were mixed. Mass of yellow bullhead, rainbow trout and brown trout declined in the removal reach from 2007 through 2012, but there was no change in smallmouth bass. Concurrently, mass of Rainbow trout, yellow bullhead and smallmouth bass did not change at reference sites, but brown trout mass declined, indicating factors other than removal were driving abundance of brown trout. Occurrence of several large flathead catfish Pylodictis olivaris in the removal reach in 2012 changed what would have been a decline in overall nonnative mass to no change over the course of the study. Spikedace Meda fulgida was the only native species positively responding to predator removal. Results of this study suggest that with moderate effort and resources applied systematically, mechanical removal can benefit some native fish species, but movement of problem species from surrounding areas into removal reaches necessitates continued control efforts. Copyright © 2014 John Wiley & Sons, Ltd.     

Polymer electrolyte membranes from fluorinated polyisoprene-block-sulfonated polystyrene: Microdomain orientation by external field

In this study, block copolymer ionomers of the cesium salt (20 mol %) of fluorinated polyisoprene-block-sulfonated polystyrene were spin cast into membranes and annealed under an electric field of ∼40 V/μm at 130 °C for 24 h. The effect of this treatment was a 2.5 times increase in the ionic conductivity as measured by electrochemical impedance spectroscopy, under all humidity conditions measured. This can be attributed to the increased connectivity of the ionic domains of the block copolymers. This E-field alignment technique may thus find application in the fabrication of nanostructured polyelectrolytes with enhanced charge transport capacity.     

Polymer electrolyte membranes from fluorinated polyisoprene-block-sulfonated polystyrene: Membrane structure and transport properties

With a view to optimizing morphology and ultimately properties, membranes have been cast from relatively inexpensive block copolymer ionomers of fluorinated polyisoprene-block-sulfonated polystyrene (FISS) with various sulfonation levels, in both the acid form and the cesium neutralized form. The morphology of these membranes was characterized by transmission electron microscopy and ultra-small angle X-ray scattering, as well as water uptake, proton conductivity and methanol permeability within the temperature range from 20 to 60 °C. Random phase separated morphologies were obtained for all samples except the cesium sample with 50 mol% sulfonation. The transport properties increased with increasing degree of sulfonation and temperature for all samples. The acid form samples absorbed more water than the cesium samples with a maximum swelling of 595% recorded at 60 °C for the acid sample having 50 mol% sulfonation. Methanol permeability for the latter sample was more than an order of magnitude less than for Nafion 112 but so was the proton conductivity within the plane of the membrane at 20 °C. Across the plane of the membrane this sample had half the conductivity of Nafion 112 at 60 °C.     

Valuation of electricity swing options by multistage stochastic programming

Electricity swing options are Bermudan-style path-dependent derivatives on electrical energy. We consider an electricity market driven by several exogenous risk factors and formulate the pricing problem for a class of swing option contracts with energy and power limits as well as ramping constraints. Efficient numerical solution of the arising multistage stochastic program requires aggregation of decision stages, discretization of the probability space, and reparameterization of the decision space. We report on numerical results and discuss analytically tractable limiting cases.     

Dispersal drives changes in fish community abundance in intermittent stream networks

Increasing trends in fragmentation and dewatering of streams warrants research on how populations and communities respond to varying water levels and barriers to movement. Although these responses are complicated by many spatial and temporal processes, long‐term datasets might help reveal complex patterns and processes driving variability in species abundances. The objective of this study was to develop a predictive framework for fish community and population responses to varying levels of water availability across six sites in two intermittent stream networks sampled >10 years. We predicted that fishes would emigrate into intermittent reaches during wet conditions; thus, overall abundances within perennial source locations will decline. Accordingly, when intermittent reaches dry, fishes will contract to wetted habitats resulting in high abundance. Observed fish community abundances were highly variable within and among study sites, but four of six sites matched our predictions. A tagging study confirmed these results and demonstrated a substantial proportion of individuals moved away from perennial reaches and into newly wetted intermittent reaches. However, site and species‐specific relationships were variable and likely depended on the habitat, metacommunity dynamics, and life history strategies. Findings suggest that species dispersal dynamics, in addition to recruitment and mortality, should be carefully considered when interpreting species responses to varying water levels, particularly in intermittent stream networks where access to habitat can change drastically with water availability.     

Long‐term Dynamics of Large‐bodied Fishes Assessed from Spatially Intensive Monitoring of a Managed Desert River

Imperilment of native fishes worldwide, and particularly in the American Southwest, has prompted management actions to protect and recover threatened populations. Implementation of management activities, however, often proceeds without clear understandings of ecological interactions between native fishes and other biotic and physical components of the environment. Using data obtained in a 19‐year, intensive monitoring effort across 288 km of the San Juan River in NM and UT, USA, we quantified relationships among large‐bodied fishes and longitudinal environmental gradients, tested for faunal breaks of fishes and habitat structure along the river's course, and assessed the response of fishes to mechanical removal of non‐native fishes and stocking of endangered fishes. Mesohabitat variation was not strongly linked to densities of large‐bodied fishes, but we found strong and temporally consistent longitudinal patterns of native and non‐native fishes: Native fish densities were highest upstream while non‐native fish densities where highest downstream, potentially driven by differential responses to temperature regimes. Two breaks in the longitudinal structure of large‐bodied fishes were identified and were associated with a man‐made barrier and changes in the width of the river's floodplain. While densities of common native fishes were relatively constant during the study, non‐native fish removal apparently reduced densities of one of two targeted species and densities of two endangered fishes increased as a result of stocking hatchery‐reared fish. Results of this study suggest that large‐bodied fishes of the San Juan River are responding to large‐scale longitudinal gradients rather than small‐scale habitat variation and management activities have altered densities of target species with limited responses by other fishes in the system. Copyright © 2014 John Wiley & Sons, Ltd.