Reductive hydrogenation of polycyclic aromatic hydrocarbons catalyzed by metalloporphyrins

The hydrogenation of polycyclic aromatic hydrocarbons (PAHs) (naphthalene, anthracene, and phenanthrene) catalyzed by metalloporphyrins based on cobalt, nickel or iron was studied in aqueous solutions at room temperature and ambient pressure. Nickel porphyrin (P1) activated by nanosized zero-valent iron (nano-ZVI) and cobalt porphyrins (P2) and (P4) activated by titanium(III) citrate as the electron donor were demonstrated to be promising catalysts for the reductive hydrogenation of PAHs. In particular, partially saturated di-, tetra-, and octahydrogenated products were obtained for anthracene or phenanthrene using a nickel porphyrin activated by nano-ZVI, while naphthalene was transformed to tetralin. Systems containing cobalt porphyrins activated by titanium(III) citrate exhibited a high selectivity and activity toward hydrogenation of anthracene, producing 9,10-dihydroanthracene. However, no formation of hydrogenated hydrocarbons was observed from naphthalene or phenanthrene using cobalt porphyrins.     

Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Making a life in the physical sciences

As a practicing physical chemist, I argue that the challenges faced by the physical sciences have more parallels with organization science than it might first appear. While the physical sciences do represent a strong paradigm endeavor, many of the same issues that were raised in the article “Making a life in the field of organizational science” arise in physical sciences. An essential difference between the physical sciences and organization science is the essentially capital intensive nature of our research. Ironically, the constant pursuit of the requisite research dollars leads to substantial similarity between the fields. The state of academic physical sciences is analyzed in this context informed by the current state of research funding in the United States. Copyright © 2008 John Wiley & Sons, Ltd.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Relating Background NO2 Concentrations in Air to Air Mass History Using Non-Parametric Regression Methods: Application at Two Background Sites in Ireland

The concentration of nitrogen dioxide (NO₂) in background air varies temporally and spatially and is influenced by meteorological and anthropogenic factors. Background concentrations used in local air quality modelling studies have a significant effect on the accuracy of the overall result and when based on short-term monitoring data, variation in concentrations with air mass history is often unaccounted for. The current paper presents a powerful tool for the quantification and separation of local and regional air mass effects on background air quality. The origin of and the regions traversed by an air mass prior to reaching a receptor has been modelled using HYsplit-4. Trajectories (between 12 and 96?h duration) were defined based on the frequency with which they passed into 16 predefined compass quadrants and each represented as a vector. Using this vector as the predictor variable and the background concentration as the response variable, non-parametric regression using a Gaussian kernel function was carried out. A graphical output indicated the trajectory direction of maximum NO₂ concentration, while allowing distinction to be made between spurious and true peaks. In all cases, air mass history was found to have a statistically significant effect on NO₂ concentrations. Incorporating emissions data into the analysis local and regional effects were separated and quantified. It was found that emissions in the UK and Europe have a significant effect on background NO₂ concentrations in Ireland and in some instances supersede domestic emissions. The methods can be used to identify source regions, separate local and regional effects and improve predictions of background concentrations based on limited monitoring data. In particular, the results highlight the importance of considering air mass history when assessing background concentration levels for use in local air quality modelling studies.     

Recommended metric for tracking visibility progress in the Regional Haze Rule

For many national parks and wilderness areas with special air quality protections (Class I areas) in the western United States (U.S.), wildfire smoke and dust events can have a large impact on visibility. The U.S. Environmental Protection Agency’s (EPA) 1999 Regional Haze Rule used the 20% haziest days to track visibility changes over time even if they are dominated by smoke or dust. Visibility on the 20% haziest days has remained constant or degraded over the last 16 yr at some Class I areas despite widespread emission reductions from anthropogenic sources. To better track visibility changes specifically associated with anthropogenic pollution sources rather than natural sources, the EPA has revised the Regional Haze Rule to track visibility on the 20% most anthropogenically impaired (hereafter, most impaired) days rather than the haziest days. To support the implementation of this revised requirement, the EPA has proposed (but not finalized) a recommended metric for characterizing the anthropogenic and natural portions of the daily extinction budget at each site. This metric selects the 20% most impaired days based on these portions using a “delta deciview” approach to quantify the deciview scale impact of anthropogenic light extinction. Using this metric, sulfate and nitrate make up the majority of the anthropogenic extinction in 2015 on these days, with natural extinction largely made up of organic carbon mass in the eastern U.S. and a combination of organic carbon mass, dust components, and sea salt in the western U.S. For sites in the western U.S., the seasonality of days selected as the 20% most impaired is different than the seasonality of the 20% haziest days, with many more winter and spring days selected. Applying this new metric to the 2000–2015 period across sites representing Class I areas results in substantial changes in the calculated visibility trend for the northern Rockies and southwest U.S., but little change for the eastern U.S.

Implications: Changing the approach for tracking visibility in the Regional Haze Rule allows the EPA, states, and the public to track visibility on days when reductions in anthropogenic emissions have the greatest potential to improve the view. The calculations involved with the recommended metric can be incorporated into the routine IMPROVE (Interagency Monitoring of Protected Visual Environments) data processing, enabling rapid analysis of current and future visibility trends. Natural visibility conditions are important in the calculations for the recommended metric, necessitating the need for additional analysis and potential refinement of their values.     

Supervisor expediency to employee expediency: The moderating role of leader–member exchange and the mediating role of employee unethical tolerance

We utilize social learning theory to test the role‐modeling effect of supervisor expediency (i.e., a supervisor's use of unethical practices to expedite work for self‐serving purposes). In particular, we examine the relationship between supervisor expediency and employee expediency, as moderated by leader–member exchange (LMX) and mediated by employee unethical tolerance. We predict that employees are more likely to model their supervisors' expedient behaviors when their relationship is characterized by high‐LMX (a high‐quality exchange relationship that is rich in socioemotional support). Furthermore, we argue that supervisor expediency, especially when LMX is high, influences employees' attitudes of unethical tolerance, which then affects employees' expedient behaviors. Across 2 multisource field studies and a third time‐lagged field study, we found general support for our theoretical predictions. Theoretical and practical implications are discussed.     

The Use of Subbottom Profiling in Refining Dredge Cuts for a Large‐Scale Sediment Remediation Project

A number of different techniques were employed to locate the target dredge grade on a large‐scale Canadian sediment remediation project. These techniques included various coring events, Seabed Terminal Impact Newton Gradiometer (STING) testing, and geotechnical borings. Despite these techniques, the data set for interpolation of the dredge grade was widely spaced, and some of the investigations were not specifically intended to be used for defining the dredge grade. In order to reduce the risk of extra expenses from contractor claims resulting from differing sediment conditions, more precise planning was required. Due to the size of the area and the desired accuracy, subbottom profiling was identified as a potential tool to provide high‐density coverage across the site. As with any geophysical tool, ground truth data were required to verify and aid in interpretation. This article describes how subbottom profiling was used to refine the dredge grade for the target layer, the associated challenges related to signal loss in some areas, and how they were overcome. ©2017 Wiley Periodicals, Inc.     

Marginal abatement cost curve for nitrogen oxides incorporating controls,renewable electricity,energy efficiency,and fuel switching

A marginal abatement cost curve (MACC) traces out the relationship between the quantity of pollution abated and the marginal cost of abating each additional unit. In the context of air quality management, MACCs are typically developed by sorting control technologies by their relative cost-effectiveness. Other potentially important abatement measures such as renewable electricity, energy efficiency, and fuel switching (RE/EE/FS) are often not incorporated into MACCs, as it is difficult to quantify their costs and abatement potential. In this paper, a U.S. energy system model is used to develop a MACC for nitrogen oxides (NO_x) that incorporates both traditional controls and these additional measures. The MACC is decomposed by sector, and the relative cost-effectiveness of RE/EE/FS and traditional controls are compared. RE/EE/FS are shown to have the potential to increase emission reductions beyond what is possible when applying traditional controls alone. Furthermore, a portion of RE/EE/FS appear to be cost-competitive with traditional controls.

Implications: Renewable electricity, energy efficiency, and fuel switching can be cost-competitive with traditional air pollutant controls for abating air pollutant emissions. The application of renewable electricity, energy efficiency, and fuel switching is also shown to have the potential to increase emission reductions beyond what is possible when applying traditional controls alone.