Identification of transport processes in column experiments using a frequency domain approach

When a solute transport process is viewed as a dynamic system with input and output, a system identification technique can be used to study it from input-output data. According to the design of excitation signals in the system identification approach, the commonly used rectangular pulse as input signal for column experiments is not optimum because it does not simultaneously meet the requirements for exciting the studied transport process, i.e., possessing frequency components with high enough amplitude and wide enough passband. In this article, stepped sine signals were proposed to replace the rectangular pulse because their amplitude and passband can be independently chosen. The stepped sine signals of concentration were generated by a High Performance Liquid Chromatography (HPLC) and used as the input for the column experiments to identify parameters of the convection-dispersion equation (CDE) and mobile-immobile model (MIM). In order to test the effect of noise on the identification of transport process, numerical experiments were carried out to identify the CDE under white noise when the input was designed as stepped sine functions and rectangular pulse. The results of the numerical experiments showed that the input signal of a sine function was more robust and accurate in process identification than that of a rectangular pulse.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

Source apportionment of fine particulate matter in the southeastern United States

Particulate matter (PM) less than 2.5 microm in size (PM2.5) source apportionment by chemical mass balance receptor modeling was performed to enhance regional characterization of source impacts in the southeastern United States. Secondary particles, such as NH4HSO4, (NH4)2SO4, NH4NO3, and secondary organic carbon (OC) (SOC), formed by atmospheric photochemical reactions, contribute the majority (>50%) of ambient PM2.5 with strong seasonality. Source apportionment results indicate that motor vehicle and biomass burning are the two main primary sources in the southeast, showing relatively more motor vehicle source impacts rather than biomass burning source impacts in populated urban areas and vice versa in less urbanized areas. Spatial distributions of primary source impacts show that each primary source has distinctively different spatial source impacts. Results also find impacts from shipping activities along the coast. Spatiotemporal correlations indicate that secondary particles are more regionally distributed, as are biomass burning and dust, whereas impacts of other primary sources are more local.     

Bacterial community structure in soils contaminated by polycyclic aromatic hydrocarbons

Bacterial community structure was examined in polycyclic aromatic hydrocarbon (PAH) contaminated soil taken from a timber treatment facility in southern Ireland. Profiles of soil bacterial communities were generated using a molecular fingerprinting technique, terminal restriction fragment length polymorphism (TRFLP), and results were interpreted using sophisticated multivariate statistical analysis. Findings suggested that there was a correlation between PAH structure and bacterial community composition. Initial characterisation of soil from the timber treatment facility indicated that PAH contamination was unevenly distributed across the site. Bacterial community composition was correlated with the type of PAH present, with microbial community structure associated with soil contaminated with two-ringed PAHs only being distinctly different to communities in soils contaminated with multi-component PAH mixtures. Typically the number of bacterial ribotypes detected in samples did not appear to be adversely affected by the level of contamination.     

Partitioning and removal of perfluorooctanoate during rain events: the importance of physical-chemical properties

The potential for airborne emissions to undergo long-range transport or to be removed from the atmosphere is influenced by their physical-chemical properties. When perfluorooctanate (PFO) enters the environment, its physical-chemical properties can vary significantly, depending on whether it exists as an acid, a salt, or a dissociated ion. A summary of the physical-chemical properties of the three most likely environmental states: ammonium perfluorooctanoate (APFO), perfluorooctanoic acid (PFOA) and the dissociated perfluorooctanoate anion (PFO(-)) is presented to illustrate the distinct environmental properties of each. The most volatile species, PFOA, is shown to have a pH-dependent air-water partitioning coefficient (K(aw)). The variability of K(aw) with pH influences the potential for vapor formation from aqueous environments, including rain events. Using the pH-dependent K(aw) and measured rain and air concentrations, it is shown that vapor-phase PFOA is not likely to be present above measurable levels of 0.2 ng m(-3) (12 parts per quadrillion v/v) during a rain event. Because rain concentrations determined in this work are comparable to measurements in other parts of North America, it is unlikely that rain events are a significant source of vapor-phase PFOA for the general North American region. It is shown that PFOA exists primarily in the particle phase in ambient air near direct sources of emissions and is efficiently scavenged by rain droplets, making wet deposition an important removal mechanism for emissions originating as either PFOA or APFO. Washout ratios of particle-associated PFO were determined to range between 1 x 10(5) and 5 x 10(5), in the same range as other semi-volatile compounds for which wet deposition is an important mechanism for atmospheric removal and deposition onto soils and water bodies.     

Empirical analysis of shared leadership promotion and team creativity: An adaptive leadership perspective

Promoting shared leadership in teams and enhancing team creativity is aided by complementarity between leader and team member characteristics. We integrate insights from social learning theory and dominance complementarity perspective with the team leadership and creativity literature to explore the facilitating role of formal participative leadership for enhancing team creativity indirectly by promoting shared leadership. The relationships among formal participative leadership, shared leadership, and team creativity are bounded by team voice behavior and team creative efficacy. To test our theoretical model, we collected multisource and multiwave survey data from 382 members of 73 teams. Results revealed a significant positive relationship of participative leadership with shared leadership in teams, which in turn was positively associated with team creativity. Team voice behavior and team creative efficacy moderated these relationships, respectively, by strengthening the positive relationships. We discuss the theoretical contributions, practical implications, and future directions of our findings.     

The distribution and composition of hydrocarbons in sediments from the Fladen Ground, North Sea, an area of oil production

The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.     

The evolution of the Canadian mining industry: The role of regulatory punctuation

In this study, we analyze the evolution of Canada's mining industry from 1929 to 2006, focussing on the determinants of the number of firms in the industry and why this number changed over that period. Most empirical studies of industry evolution have focused on manufacturing industries that share similar structural characteristics. Perhaps because of this, extant models of industry evolution tend to ignore industry-specific and national-specific factors that can cause atypical trajectories, that is, heterogeneous industry evolution. Initial inspection of the Canadian mining industry shows that it is atypical in that it exhibits “negative skew” over time in the number of firms rather than the typical “positive skew.” We review two dominant theoretical approaches to industry evolution: the density-dependence theory and variants of industrial organization economics. We also consider possible sources of industry evolution heterogeneity, focussing particularly on “regulatory punctuation”. Using Canadian mining data, we find that the traditional models do not fully explain the changes in population size in Canada's mining industry. As a result, we introduce a number of hybrid models. The results from these hybrid models suggest that Canadian-specific regulatory punctuations, particularly the introduction of significant new taxes, environmental legislation, and incentives have shaped the trajectory of mining firm participation.     

Plasma versus Thermal Effects in Flue Gas NOx Reduction Using Ammonia Radical Injection

Abstract

A plasma-assisted ammonia injection technique was previously demonstrated as having the potential to remove NO_x from combustion flue gases at SCR-comparable levels without the use of catalysts. However, these demonstrations did not prove the advantage of plasma assistance because they did not explicitly account for enhanced radical production by bulk thermal heating. An experiment using hot ammonia injection was performed to separate this thermal effect from the effect of radical production via interaction with a plasma. Under excess air conditions, results show that a thermal effect does provide improved NO_x reduction, but not to the level achieved with the use of a plasma source. However, heating the injection gases provides only a minor improvement in NO_x reduction at NH₃/NO_x ratios and temperatures typical of commercial cold SNCR applications. The plasma effect in ammonia radical injection was also found to be significant, accounting for an additional 15% to 35% of absolute NO_x reduction beyond any thermal benefit at typical excess air conditions. The ammonia radical injection technique continues to show promise as an effective NO_x reduction alternative.