Isomeric analysis of PCDD/PCDF in waste incinerator fly ash by GC-MS/MS

The development of an analytical method for the analysis of PCDD/PCDF in flyash using a bench analytical system comprising of a gas chromatograph fitted with an ion trap detector operated in the tandem MS mode is described. The optimum settings for the most important MS/MS parameters are given, including those for the less reported mono- to tri-chlorinated dioxin and furan congener groups. Flyash samples from three waste incineration plants representing a decommissioned 1970s plant design, an upgraded and still operating plant originally designed in the 1970s, and a modern 1990s design operating plant have been analysed for PCDD/PCDF. The flyash samples were analysed for PCDD/PCDF using the methods developed and the total PCDD/PCDF, I-TEQ values and isomeric profiles are reported. The flyash from the older decommissioned incinerator had very significantly higher concentrations of PCDD/PCDF compared to the modern incinerator flyash.     

Sorption of organic compounds to activated carbons. Evaluation of isotherm models

Sorption to ‘hard carbon’ (black carbon, coal, kerogen) in soils and sediments is of major importance for risk assessment of organic pollutants. We argue that activated carbon (AC) may be considered a model sorbent for hard carbon. Here, we evaluate six sorption models on a literature dataset for sorption of 12 compounds onto 12 ACs and one charcoal, at different temperatures (79 isotherms in total). A statistical analysis, accounting for differences in the number of fitting parameters, demonstrates that the dual Langmuir equation is in general superior and/or preferable to the single and triple Langmuir equation, the Freundlich equation, a Polanyi–Dubinin–Manes equation, and the Toth equation. Consequently, the analysis suggests the presence of two types of adsorption sites: a high-energy (HE) type of site and a low-energy (LE) type of site. Maximum adsorption capacities for the HE domain decreased with temperature while those for the LE domain increased. Average Gibbs free energies for adsorption from the hypothetical pure liquid state at 298 K were fairly constant at −15 ± 4 and −5 ± 4 kJ mol⁻¹ for the HE and LE domain, respectively.     

Determination and distribution characteristics of degradation products of nonylphenol polyethoxylates in the rivers of Taiwan

Concentrations of degradation products of nonylphenol polyethoxylates (NPEOs) were analyzed in river water samples in order to determine the distribution characteristic of these alkylphenolic compounds in 18 major rivers of Taiwan. The degradation products of NPEOs were detected in all river samples, with the dicarboxylates alkylphenolic degradation products (CAPEC) being detected most frequently and at the highest concentrations. Concentrations of NP and NP1EO in rivers ranged from n.d. to 5.1 μg l⁻¹ and n.d. to 0.5 μg l⁻¹, respectively. The total concentrations of shortened carboxylates (i.e., NP1EC + NP2EC + NP3EC) and dicarboxylates alkylphenolic degradation products (CAP1EC + CAP2EC) ranged from n.d. to 63.6 μg l⁻¹ and n.d. to 94.6 μg l⁻¹, respectively. Concentrations of NP2EC, NP3EC and all CAPEC residues were determined semi-quantitatively by comparing with the internal standard. Significantly higher concentrations of CAPEC residues were detected in the river waters as compared to those of NP, NP1EO and NPEC degradation products and the average proportions of these compounds in the samples of the rivers were as follows: NP + NP1EO was 5 ± 2.5%, total NPEC was 25 ± 12%, and total CAPEC was 70 ± 12%. The high concentration ratios of CAPEC/NPEC illustrate that aerobic biodegradation plays a main route in the fate of NPEO in the rivers of Taiwan.     

Characterization of polycyclic aromatic hydrocarbons in urban stormwater runoff flowing into the tidal Anacostia River, Washington, DC, USA

To investigate the sources, fate, and transport dynamics of PAHs (polycyclic aromatic hydrocarbons) in stormwater runoff that is a leading source of pollution in urban watersheds, storm and base flow samples were collected in six branches along the lower Anacostia River. PAHs in storm flow (1510-12,500 ng/L) were significantly enriched in the particle phase, which accounted for 68-97% of the total PAHs. It suggests that reducing particles in stormwater using post-treatment system would decrease PAHs considerably. The solid-water distribution coefficients (KD) of PAHs in the storm flow samples were up to 340 times higher than predicted values. A greater portion of high molecular weight PAHs and their distribution patterns indicate higher contribution of automobile originated pyrogenic PAHs. Total suspended solids in storm flow had a positive relationship with flow rates and exceeded benchmark level for the protection of aquatic biota in some samples.     

Model-Based Assessment of Aspen Responses to Elk Herbivory in Rocky Mountain National Park,USA

In Rocky Mountain National Park (RMNP), aspen (Populus tremuloides Michx.) has been observed to be declining on elk (Cervus elaphus nelsoni) winter range for many decades. To support elk management decisions, the SAVANNA ecosystem model was adapted to explore interactions between elk herbivory and aspen dynamics. The simulated probability of successful vegetative regeneration for senescent aspen stands declines sharply when elk densities reach levels of 3–5 elk/km², depending on model assumptions for the seasonal duration of elk foraging activities. For aspen stands with a substantial component of younger trees, the simulated regeneration probability declines more continuously with increasing elk density, dropping below 50% from densities at 8–14 elk/km².At the landscape scale, simulated aspen regeneration probability under a scenario of extensive seasonal use was little affected by elk population level, when this level was above 300–600 elk (25%–50% current population) over the ca. 107 km² winter range. This was because elk distribution was highly aggregated, so that a high density of elk occupied certain areas, even at low population levels overall. At approximately current elk population levels (1000–1200 elk), only 35%–45% of senescent aspen stands are simulated as having at least a 90% probability of regeneration, nearly all of them located on the periphery of the winter range. Successful management for aspen persistence on core winter range will likely require some combination of elk population reduction, management of elk distribution, and fencing to protect aspen suckers from elk browsing.     

UNIT HYDROGRAPHS DERWED FROM THE NASH MODEL1

ABSTRACT: Unit hydrograph ordinates are often estimated by deconvoluting excess rainfall pulses and corresponding direct runoff. The resulting ordinates are given at discrete times spaced evenly at intervals equal to the duration of the rainfall pulse. If the new duration is not a multiple of the parent duration, hydrograph interpolation is required. Linear interpolation, piece-wise nonlinear interpolation and graphical smoothing have been used. These interpolation schemes are expedient but they lack theoretical basis and can lead to undesirable results. Interpolation can be avoided if the instantaneous unit hydrograph (IUH) for the watershed is known. Here two issues connected with the classic Nash IUH are examined: (1) how should the Nash parameters be estimated? and (2) under what conditions is the resulting hydrograph able to reasonably represent watershed response? In the first case, nonlinear constrained optimization provides better estimates of the IUH parameters than does the method of moments. In the second case, the Nash IUH gives good results on watersheds with mild shape unit hydrographs, but performs poorly on watersheds having sharply peaked unit hydrographs. Overall, in comparison to empirical interpolation alternatives, the Nash IUH offers a theoretically sound and practical approach to estimate unit hydrographs for a wide variety of watersheds.     

Development of a Model for Simulation of Solute Transport in a Stream–Aquifer System

A model for simulation of solute transport in a dynamic stream–aquifer system is developed by integrating four existing sub-models. Interface packages are created to link the sub-models. The developed model is successfully used to simulate chloride transport in the stream–aquifer system of the Arkansas River and the Equus Beds Aquifer in Kansas and demonstrates that chloride concentration in the aquifer decreases in the vicinity of the simulated channel over time.     

A meta‐analysis of the antecedents of work–family enrichment

This study meta‐analytically examined theoretically derived antecedents of both directions of work–family enrichment (sometimes labeled facilitation or positive spillover), namely, work–family enrichment and family–work enrichment. Contextual and personal characteristics specific to each domain were examined. Resource‐providing (e.g., social support and work autonomy) and resource‐depleting (e.g., role overload) contextual characteristics were considered. Domain‐specific personal characteristics included the individuals' psychological involvement in each domain, the centrality of each domain, and work engagement. Results based on 767 correlations from 171 independent studies published between 1990 and 2016 indicate that several contextual and personal characteristics have significant relationships with enrichment. Although those associated with work tend to have stronger relationships with work–family enrichment and those associated with family tend to have stronger relationships with family–work enrichment, several antecedent variables have significant relationships with both directions of enrichment. Resource‐providing contextual characteristics tend to have stronger relationships with enrichment than do resource‐depleting characteristics. There was very little evidence of gender being a moderator of relationships between contextual characteristics and enrichment. Lastly, meta‐analytic structural equation modeling provided evidence that a theoretical path model wherein work engagement mediates between several contextual characteristics and enrichment is largely generalizable across populations.     

Antecedents and consequences of satisfaction with work–family balance: A moderating role of perceived insider status

This study developed a moderated mediation model to investigate how family‐supportive paid leave and supervision affect employees' satisfaction with work–family balance and in turn their affective organizational commitment and supervisor‐directed organizational citizenship behavior depending on their perceived insider status in the organization. Our analysis of data collected from 118 employee–supervisor dyads in Korean organizations revealed that satisfaction with work–family balance mediated the linkages from family‐supportive supervision to affective organizational commitment and supervisor‐directed organizational citizenship behavior, and the linkage from family‐supportive paid leave to affective organizational commitment. Results further showed that the entire mediational process for family‐supportive supervision was more pronounced for those who perceived themselves to be an insider of their organizations, while the same pattern was not found for the meditational process related to family‐supportive paid leave. Our findings provide theoretical implications for work–family balance research and offer practical suggestions to make employees satisfied with work–family balance.     

Examining the interpersonal process and consequence of leader–member exchange comparison: The role of procedural justice climate

Individuals are always sensitive to their relative standing in interpersonal comparison processes of leader–member exchanges (LMXs) in teams. Little research, however, has investigated whether coworkers with a higher LMX influence the emotional and behavioral reactions of individuals with a lower LMX in different dyads. Drawing on social comparison theory and the symbolic model of procedural justice (PJ) climate, we conducted 2 independent studies—an experimental study focusing on the self‐perceived upward LMX comparison (i.e., an individual perceives that a coworker's LMX is higher than the LMX that he or she has with the supervisor; N = 203; Study 1: American working adults) and a field survey study focusing on the other‐perceived downward LMX comparison (i.e., a coworker perceives that his or her own LMX is higher than the LMX that the individual has with the supervisor; N = 177; Study 2: Chinese software engineers). Results from these studies consistently revealed that a coworker's higher LMX elicits an individual's hostile emotions when the PJ climate is low but that this relationship is buffered when the PJ climate is high. Results of both studies also showed that the coworker's higher LMX arouses the individual to direct harmful behavior toward that coworker (via the individual's feelings of hostility) when the PJ climate is low but not when it is high.