Mechanochemistry of phosphate esters confined between sliding iron surfaces

The molecular structure of lubricant additives controls not only their adsorption and dissociation behaviour at the nanoscale, but also their ability to reduce friction and wear at the macroscale. Here, we show using nonequilibrium molecular dynamics simulations with a reactive force field that tri(s-butyl)phosphate dissociates much faster than tri(n-butyl)phosphate when heated and compressed between sliding iron surfaces. For both molecules, dissociative chemisorption proceeds through cleavage of carbon−oxygen bonds. The dissociation rate increases exponentially with temperature and stress. When the rate−temperature−stress data are fitted with the Bell model, both molecules have similar activation energies and activation volumes and the higher reactivity of tri(s-butyl)phosphate is due to a larger pre-exponential factor. These observations are consistent with experiments using the antiwear additive zinc dialkyldithiophosphate. This study represents a crucial step towards the virtual screening of lubricant additives with different substituents to optimise tribological performance

Identifying Effects and Applications of Fixed and Variable Speed Limits

In Indiana, distracted driving and unexpected queues have led to an increase in the amount of back-of-queue crashes, particularly on approach to work zones. This report presents new strategies for the assessment of both transportation safety and traffic operations using crowd-sourced probe vehicle data and a speed laser vehicle re-identification scheme. This report concludes by recommending strategies for the placement of variable speed limits (VSL) adjacent to work zones and suggestions for future research

Algae Drive Enhanced Darkening of Bare Ice on the Greenland Ice Sheet

Surface ablation of the Greenland ice sheet is amplified by surface darkening caused by light-absorbing impurities such as mineral dust, black carbon, and pigmented microbial cells. We present the first quantitative assessment of the microbial contribution to the ice sheet surface darkening, based on field measurements of surface reflectance and concentrations of light-absorbing impurities, including pigmented algae, during the 2014 melt season in the southwestern part of the ice sheet. The impact of algae on bare ice darkening in the study area was greater than that of nonalgal impurities and yielded a net albedo reduction of 0.038 ± 0.0035 for each algal population doubling. We argue that algal growth is a crucial control of bare ice darkening, and incorporating the algal darkening effect will improve mass balance and sea level projections of the Greenland ice sheet and ice masses elsewhere

Mineral phosphorus drives glacier algal blooms on the Greenland Ice Sheet

Melting of the Greenland Ice Sheet is a leading cause of land-ice mass loss and cryosphere-attributed sea level rise. Blooms of pigmented glacier ice algae lower ice albedo and accelerate surface melting in the ice sheet’s southwest sector. Although glacier ice algae cause up to 13% of the surface melting in this region, the controls on bloom development remain poorly understood. Here we show a direct link between mineral phosphorus in surface ice and glacier ice algae biomass through the quantification of solid and fluid phase phosphorus reservoirs in surface habitats across the southwest ablation zone of the ice sheet. We demonstrate that nutrients from mineral dust likely drive glacier ice algal growth, and thereby identify mineral dust as a secondary control on ice sheet melting.SCOPUS: ar.jinfo:eu-repo/semantics/publishe

Characterizing Reliability of Manual Intersection Turning Movement Counts Using Modern Data Collection Technology

Collecting intersection turning movement counts at intersections is an essential data collection task for many types of traffic engineering studies. On a daily basis, consulting firms and agencies collect turning movement counts that are used for preparing traffic impact studies, determining design hours for road improvements, and the retiming of traffic signals. Although there is a substantial body of literature on the stochastic nature of traffic volumes and how they vary by time, day of week, and season, the literature is quite sparse on how accurately turning movement counts can be collected at signalized intersections. The objective of this paper is to characterize the reliability of manual intersection turning movement counts performed with modern data collection technology. Live intersection turning movement counts were performed on three days for three hours to characterize the range and reliability of percent errors. Every user, regardless of interface or device, improved from the first day to the second day, and all but one improved again between the second and third day. There was no clear superior data collection technology, but with the emerging ubiquitous of smart phones and tablets, the cost –benefit of these devices has the potential to change the manual counting techniques of the future. Traffic counter software running on smart phones or consumer electronic devices has the benefit of being affordable and perhaps more convenient as an electronic counting device (ECD)

An Asset Management Framework for Addressing the New MUTCD Traffic Sign Retroreflectivity Standards

The 2009 Manual on Uniform Traffic Control Devices (MUTCD) requires that all agencies implement traffic sign management programs by January 8th, 2012. Most agencies are expected to adopt some type of systematic replacement policy based on life expectancy, augmented by visual inspection to identify signs with obvious damage. Several previous efforts have developed models based on average degradation of the retroreflective sheeting as the signs age. This paper develops a series of survival curves characterizing the percent of signs that pass the retroreflectivity standards for signs ranging from 0 to 20 years. The curves representing expected conformance with the retroreflectivity standards (survival curves) are believed of greater use than previous degradation curves of average retroreflectivity. A framework for using these survival curves for red, white, and yellow backgrounds, in conjunction with local cost information, is presented to aid in the development of sign management programs. A model with sample calculations that reflect sign costs and life expectancy is developed to assist agencies in evaluating the implications of selecting alternative sheeting types and corresponding replacement schedules. The paper concludes that based on the longer warranty, the larger proportion of signs meeting the MUTCD minimums at their warranty age, and the annual cost over the warranty period that Type III High Intensity Beaded sheeting performs better than Type I Engineering Grade Beaded sheeting and has an overall lower annual cost to the agency. The paper documents the cost data and survival assumption so that local agencies can apply the model with local cost data to determine if our conclusions are consistent with local data

Physiological, biochemical and ultrastructural responses of the green macroalga Urospora penicilliformis from Arctic Spitsbergen to UV radiation

Exposure of the filamentous turf green alga Urospora penicilliformis to ambient and artificial ultraviolet radiation (UVR) revealed a considerable resilient species. This explains the ability of this alga to thrive in the middleupper intertidal zones of the Arctic sea where it is periodically exposed to environmental extremes. A transient UVR effect on photosynthesis under photosynthetically active radiation (PAR) + UV-A and PAR + UV-A + UV-B was found, but dynamic recovery of photoinhibition was observed immediately after reduction of the photon fluence rate of PAR in the absence or presence of background UVR under laboratory and natural solar radiation, respectively. Chlorophylls, carotenoids, and xanthophyll cycle pigments (violaxanthin, antheraxanthin, and zeaxanthin) concentrations were not significantly different between freshly collected samples and filaments exposed to additional laboratory radiation treatment. The ultrastructure of the U. penicilliformis gametophytes showed that the cells are well adapted to UVR. No significant ultrastructural alterations were observed in filaments exposed to different spectral irradiance in the laboratory compared to in situ acclimated specimen. The antioxidant α-tocopherol was detected in minute quantity while the search for flavonoid-like compounds was negative. Other UV screening strategies or certain genetically fixed physiological protective mechanism could be operating in this species responsible for their occurrence in higher shoreline and ecological success. Further molecular and biochemical studies are needed to elucidate the stress resistance in this turf alga. There is an indication that the extremely thick cell wall of U. penicilliformis gametophytes covered with mucilage sheath and dense layer of mineral depositions may provide a shield against unfavorable environmental conditions in general and against UVR in particular

Effects of realistically simulated, elevated UV irradiation on photosynthesis and pigment composition of the alpine snow alga Chlamydomonas nivalis and the arctic soil alga Tetracystis sp. (Chlorophyceae).

An indoor sun simulator was used to provide elevated UV-B radiation (280-315 nm) in combination with realistic ratios to PAR (400-700 nm) and UV-A radiation (315-400 nm) in order to test the physiological response of a soil- and snow microalga during a three-day stress scenario, which may occasionally occur in their respective arctic and alpine habitats. Chlamydomonas nivalis and Tetracystis sp. are initial colonizers of harsh habitats like summer snow fields and bare arctic soils. The two species were chosen because of their role as primary successors in places where life is generally limited by extreme climatic and nutritional conditions. The influence of the increased UV-B irradiation (1.43 W m(-2); control: 0.52 W m(-2)) on photosynthesis and pigment composition was measured. Both species survived this incubation without any morphological signs of damage, but oxygen production was reduced by 20-56%. Under control conditions, the amount of chlorophylls (Chls) and carotenoids (Cars) per dry mass increased after three days due to optimal light conditions. After the same period, the treated samples of the soil alga Tetracystis sp. showed a smaller increase in Chls and primary Cars than the control. However, the production of extraplastidal, secondary Cars was induced. On the contrary, the snow alga C. nivalis already had high amounts of secondary Cars before the experiment, and after exposure, all pigment classes increased more compared to control conditions. The results show that these microalgae can tolerate short episodes of enhanced UV-B radiation. Photosynthesis may be temporally impaired, but the cells respond by the production of secondary Cars, which can shield their chloroplasts against excessive irradiation or quench reactive oxygen species