Control of Contaminant Emissions From Fossil Fuel-Fired Boilers

The importance of fuels combustion was brought into sharp focus recently in a report on air pollution to the United States Senate in which it was stated, “These processes replace usable air with potentially harmful pollutants, and the capability of the atmosphere to disperse and dilute these pollutants—especially in urban areas where people, vehicles, and industries congregate in even greater numbers—is strictly limited.”¹ The overwhelming burden of emissions of sulfur compounds, as well as nitrogen compounds and particulate matter in the U. S. today, originates from the burning of coal and fuel oil in stationary combustion sources. Thus, combustion has a large influence on the quality of the atmosphere in most urban areas. The air pollution effects of these contaminants are many and varied and all are objectionable and undesirable. Without a doubt, the most serious air pollution problem in the nation today is that created by the combustion of fossil fuels.     

Mathematical Modeling of Photochemical Smog Using the PICK Method

A new method for solving the turbulent atmospheric diffusion equation has been developed based on Lagrangian mass points, or particles moving through an Eulerian grid. The method is one of a family of Particle-/n-Cell techniques but is a unique extension to incorporate the effects of turbulent diffusion based on K-theory; thus the acronym PICK.

In the three-dimensional computer-aided model, NEXUS (Numerical EXamination of Urban Smog), this method has been applied to simulation of carbon monoxide (CO) in Los Angeles. For CO the NEXUS simulation was within 20% of observed day-averaged concentrations at 12 stations and the hour-averages were also in good agreement. This model was extended to include the effects of photochemical smog in Los Angeles. The results of the photochemical simulation were also qualitatively correct due to rapid NO to NO₂ conversion in the simulation.     

A Method for Predicting the Effective Volume Resistivity of a Sodium Depleted Fly Ash Layer

Research has been conducted to develop a technique for predicting the effective volume resistivity of a fly ash layer that has been exposed to circumstances leading to a hot-side precipitator problem known as sodium depletion. Eight fly ashes, representing a major portion of U.S. coals, were evaluated by subjecting 0.5 cm ash layers to a continuously applied voltage gradient of 4 kV/cm for periods of time up to 35 days at a temperature of 350°C (662°F). Resistivity was determined at 350°C before the test started and after the long period of applied voltage used to create the sodium depleted situation. In this condition, resistivity was also determined at 280°C (536°F) for an average electric field Intensity of 4 kV/cm and immediately prior to breakdown. This experimental method can be used with any ash sample to estimate resistivity In a sodium depleted condition. But in addition, a correlation resulting from these resistivity data has been developed. This correlation Is combined with an existing technique for predicting resistivity to produce a method for calculating the expected ash layer resistivity after sodium depletion has occurred.     

Use of Energy Scenarios in Addressing the CO2 Question

A reference scenario for CO₂ emissions was developed using a model of world energy supply and demand. In the reference scenario, world GNP and world energy demand increase at average rates of 2.1 percent per year and 1.5 percent per year, respectively during the period 1975-2100. The corresponding annual CO₂ emissions rise to a maximum of 16 gigatons of carbon around 2050 and then decline as a result of a transition to nonfossil fuel energy systems. A modified scenario for high CO₂ emissions was obtained by assuming an abundant supply of low cost coal, thus eliminating the transition. A low case was developed in which the low cost of alternative energy (i.e., solar, nuclear) induces an earlier shift away from fossil fuels.

Annual emissions of the three scenarios were used as input to a global carbon cycle model and the CO₂ buildup in the atmosphere during the period 1980-2100 was determined by the model. All three scenarios showed continuous rises in atmospheric CO₂ concentration. The reference scenario reached 775 ppm by 2100. The high CO₂ case resulted in concentrations of over 1040 ppm, and for the low case the 2100 concentration was just under 700 ppm. If the climate theory is correct, even 700 ppm is sufficient to give significant climate warming, but by experiencing the change gradually over a century, adaptation may not be painful. An early transition to nonfossil fuel supplies makes the problem less severe but does not eliminate it.     

Use of AERMOD to Determine a Hydrogen Sulfide Emission Factor for Swine Operations by Inverse Modeling

This study was conducted to determine both optimal settings applied to the plume dispersion model, AERMOD, and a scalable emission factor for accurately determining the spatial distribution of hydrogen sulfide concentrations in the vicinity of swine concentrated animal feeding operations (CAFOs). These operations emit hydrogen sulfide from both housing structures and waste lagoons. With ambient measurements made at 4 stations within 1 km of large swine CAFOs in Iowa, an inverse-modeling approach applied to AERMOD was used to determine hydrogen sulfide emission rates. CAFO buildings were treated as volume sources whereas nearby lagoons were modeled as area sources. The robust highest concentration (RHC), calculated for both measured and modeled concentrations, was used as the metric for adjusting the emission rate until the ratio of the two RHC levels was unity. Utilizing this approach, an average emission flux rate of 0.57 μg/m(2)-s was determined for swine CAFO lagoons. Using the average total animal weight (kg) of each CAFO, an average emission factor of 6.06 × 10(-7) μg/yr-m(2)-kg was calculated. From studies that measured either building or lagoon emission flux rates, building fluxes, on a floor area basis, were considered equal to lagoon flux rates. The emission factor was applied to all CAFOs surrounding the original 4 sites and surrounding an additional 6 sites in Iowa, producing an average modeled-to-measured RHC ratio of 1.24. When the emission factor was applied to AERMOD to simulate the spatial distribution of hydrogen sulfide around a hypothetical large swine CAFO (1M kg), concentrations 0.5 km from the CAFO were 35 ppb and dropped to 2 ppb within 6 km of the CAFO. These values compare to a level of 30 ppb that has been determined by the State of Iowa as a threshold level for ambient hydrogen sulfide levels.     

Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses

The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course discharging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC-MS/MS and GC-MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p'-DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 microM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones.     

Uptake and loss of dissolved 109Cd and 75Se in estuarine macroinvertebrates

Semaphore crabs (Heloecius cordiformis), soldier crabs (Mictyris platycheles), ghost shrimps (Trypaea australiensis), pygmy mussels (Xenostrobus securis), and polychaetes (Eunice sp.), key benthic prey items of predatory fish commonly found in estuaries throughout southeastern Australia, were exposed to dissolved (109)Cd and (75)Se for 385 h at 30 k Bq/l (uptake phase), followed by exposure to radionuclide-free water for 189 h (loss phase). The whole body uptake rates of (75)Se by pygmy mussels, semaphore crabs and soldier crabs were 1.9, 2.4 and 4.1 times higher than (109)Cd, respectively. There were no significant (P>0.05) differences between the uptake rates of (75)Se and (109)Cd for ghost shrimps and polychaetes. The uptake rates of (109)Cd and (75)Se were highest in pygmy mussels; about six times higher than in soldier crabs for (109)Cd and in polychaetes for (75)Se - the organisms with the lowest uptake rates. The loss rates of (109)Cd and (75)Se were highest in semaphore crabs; about four times higher than in polychaetes for (109)Cd and nine times higher than in ghost shrimps for (75)Se - the organisms with the lowest loss rates. The loss of (109)Cd and (75)Se in all organisms was best described by a two (i.e. short and a longer-lived) compartment model. In the short-lived, or rapidly exchanging, compartment, the biological half-lives of (75)Se (16-39 h) were about three times greater than those of (109)Cd (5-12h). In contrast, the biological half-lives of (109)Cd in the longer-lived, or slowly exchanging compartment(s), were typically greater (1370-5950 h) than those of (75)Se (161-1500 h). Semaphore crabs had the shortest biological half-lives of both radionuclides in the long-lived compartment, whereas polychaetes had the greatest biological half-life for (109)Cd (5950 h), and ghost shrimps had the greatest biological half-life for (75)Se (1500 h). This study provides the first reported data for the biological half-lives of Se in estuarine decapod crustaceans. Moreover, it emphasises the importance of determining metal(loid) accumulation and loss kinetics in keystone prey items, which consequently influences their trophic transfer potential to higher-order predators.     

Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.