Reducing Interference Effects in the Chemiluminescent Measurement of Nitric Oxides from Combustion Systems

Experiments were carried out to determine the relative chemiluminescence quenching efficiencies as a function of third body concentration for each of the common combustion products, H₂O, CO₂, CO, H₂, O₂ and Ar. These results are compared with those of other investigators. The effect of reaction chamber pressure on analyzer response and the development of an analyzer design which incorporates an adjustable sample capillary inlet capable of maintaining a constant molar flow rate of sample gas to the reaction chamber are discussed. The effect of carbon monoxide interference on chemiluminescent NO_x measurement has been isolated and found to be significant. A means of correcting NO, measurements for these CO interference effects is described. Quantification of NO and NO₂ absorption in liquid water in NO_x sampling systems has been made. Recommendations for sample system designs to handle the presence of water in the sample gas are made.     

Rotary Kiln Incineration II. Laboratory-Scale Desorption and Kiln-Simulator Studies—Solids

With landfill costs increasing and regulations on landfilling becoming more stringent, alternatives to conventional hazardous waste treatment strategies are becoming more desirable. Incineration Is presently a permanent, proven solution for the disposal of most organic contaminants, but also a costly one, especially in the case of solids which require some auxiliary fuel. The goal of this research is to develop an understanding of the phenomena associated with the evolution of contaminants from solids In the primary combustor of an Incineration system. A four-fold approach is being used. First, a bench-scale particle characterization reactor was developed to study the transport phenomena on a particle basis, where the controlling processes are mainly intraparticle. Second, a bed-characterization reactor was built to examine the controlling transport phenomena within a bed of particles, where the processes are primarily interparticle. The results of these studies can be applied to any primary combustor. A pilot-scale rotary kiln was developed to study the evolution of contaminants from solids within a realistic temperature and rotation environment. Finally, in situ measurements are being obtained from a full-scale rotary-kiln.

This paper describes results obtained in a study using a commercial sorbent contaminated with toluene. The data are from the particle-characterization reactor and the rotary-kiln simulator. The results show that the method of contamination and charge size do not have a large effect on desorption, while temperature and contaminant concentration are important parameters In the evolution of contaminants in a rotary kiln.     

Spatial Variation in Acidic Sulfate and Ammonia Concentrations within Metropolitan Philadelphia

Abstract

Acidic sulfate concentrations were measured in metropolitan Philadelphia during the summers of 1992 and 1993, as part of a continuing effort to characterize particle concentrations in urban environments. Sampling was performed simultaneously at eight sites located within and around metropolitan Philadelphia. Sites were selected based on their population density and on their distance and direction from the city center. Air pollution sampling was conducted every other day during the summer of 1992 and every day during the summer of 1993. All samples were collected for 24-h periods beginning at 9 a.m. (EDT). All acidic sulfate and ammonia samples were collected using modified Harvard-EPA Annular Denuder Systems (HEADS).

In this paper, we examine the spatial variation in acidic sulfate and ammonia concentrations within the metropolitan Philadelphia area. We also identify factors that may influence their variation and develop models to predict their concentrations. Outdoor sulfate (SO₄ ^2?) concentrations were uniform within metropolitan Philadelphia; however, aerosol strong acidity (H⁺) concentrations varied spatially. This variation generally was independent of wind direction, but was related to local factors, such as the NH₃ concentration, population density, and distance from the center of the city. Physico-chemical models, which were developed using data collected during the summer of 1992, were excellent predictors of 24-h and mean summertime H⁺ concentrations measured during the summer of 1993. Models accounted for 78% of the variation in 24-h H⁺ levels. Results suggest that a single stationary ambient (SAM) monitor would be sufficient to estimate SO₄ ^2? exposures for populations living in Philadelphia. For H⁺, however, multiple monitoring sites or models should be used to determine the outdoor H+ exposures of populations living in urban environments, although a single SAM site may provide an excellent index of H⁺ variation over time.     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

Aerosol Research and Inhalation Epidemiological Study (ARIES): Air Quality and Daily Mortality Statistical Modeling— Interim Results

ABSTRACT

The Aerosol Research and Inhalation Epidemiological Study (ARIES) is an EPRI-sponsored project to collect air quality and meteorological data at a single site in northwestern Atlanta, GA. Seventy high-resolution air quality indicators (AQIs) are used to examine statistical relationships between air quality and health outcome end points. Contemporaneous mortality data are collected for Fulton and DeKalb counties in Georgia. Currently, 12 months of air quality and weather data are available for analysis, from August 1998 through July 1999.

The interim mortality analysis used Poisson regression in generalized additive models (GAMs). The estimated log-linear association of mortality with various AQIs was adjusted for smoothed functions of time and meteorological data. The analysis considered daily deaths due to all nonaccidental causes, deaths to persons 65 years or older, and deaths in each of the two constituent counties. The fine particle effect associated with the four mortality subgroups, using only today (lag 0), yesterday (lag 1), 2-day average (average of today and yesterday), and first difference (today minus yesterday) measurements of the air quality relative to today's number of deaths was positive for lag 0, lag 1, and 2-day average and positive only for decedents at least 65 years of age using first difference. The t values ranged from 0.81 to 1.15 for lag 0, 1.04 to 1.53 for lag 1, 1.10 to 1.66 for 2-day average, and -0.32 to 0.33 for first difference with 346 or 347 days of data. No statistically significant estimate of the linear coefficient was found for the other 14 air quality variables in our interim analysis for the four mortality subgroups. We discuss diagnostics to support these models.

These interim analyses did not include an evaluation of sensitivity to a larger set of lag structures, nonlinear model specifications, multipollutant analyses, alternative weather model and smoothing model specifications, air pollution imputation schemes, or cause-specific mortality indicators, nor did they include a full reporting of model selection or goodness-of-fit indicators. No conclusion can be drawn at this time about whether the findings from subsequent studies have sufficiently greater power to detect effects comparable to those found in other U.S. cities including at least 2 or 3 years of data.     

Application of Forensic Techniques for Age Dating and Source Identification in Environmental Litigation

A multitude of forensic techniques are available for age dating and source identification, including corrosion models for underground storage tanks, the commercial availability of a compound, chemical associations with discrete types of manufacturing processes, chemical profiling, proprietary additives, stable isotope analysis, degradation models, biomarkers and contaminant transport models. The selection and use of these techniques in environmental litigation must be thoroughly understood and applied to be effective as forensic evidence. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to present an overview of commonly used environmental forensic techniques and their possible applications so that a user can decide which technique or combination of methods is most appropriate for their case.     

Bio-Ethanol Production from Non-Food Parts of Cassava (<Emphasis Type="Italic">Manihot esculenta</Emphasis> Crantz)

Global climate issues and a looming energy crisis put agriculture under pressure in Sub-Saharan Africa. Climate adaptation measures must entail sustainable development benefits, and growing crops for food as well as energy may be a solution, removing people from hunger and poverty without compromising the environment. The present study investigated the feasibility of using non-food parts of cassava for energy production and the promising results revealed that at least 28% of peels and stems comprise dry matter, and 10 g feedstock yields >8.5 g sugar, which in turn produced >60% ethanol, with pH ≈ 2.85, 74-84% light transmittance and a conductivity of 368 mV, indicating a potential use of cassava feedstock for ethanol production. Thus, harnessing cassava for food as well as ethanol production is deemed feasible. Such a system would, however, require supportive policies to acquire a balance between food security and fuel.     

Genetic engineering of cyanobacteria to enhance biohydrogen production from sunlight and water

To mitigate global warming caused by burning fossil fuels, a renewable energy source available in large quantity is urgently required. We are proposing large-scale photobiological H(2) production by mariculture-raised cyanobacteria where the microbes capture part of the huge amount of solar energy received on earth's surface and use water as the source of electrons to reduce protons. The H(2) production system is based on photosynthetic and nitrogenase activities of cyanobacteria, using uptake hydrogenase mutants that can accumulate H(2) for extended periods even in the presence of evolved O(2). This review summarizes our efforts to improve the rate of photobiological H(2) production through genetic engineering. The challenges yet to be overcome to further increase the conversion efficiency of solar energy to H(2) also are discussed.     

Reducing ammonia emissions from laying-hen houses through dietary manipulation

Feed additives can change the microbiological environment of the animal digestive track, nutrient composition of feces, and its gaseous emissions. This 2-yr field study involving commercial laying-hen houses in central Iowa was conducted to assess the effects of feeding diets containing EcoCal and corn-dried distillers grain with solubles (DDGS) on ammonia (NH3), hydrogen sulfide (H2S), and greenhouse gas (CO2, CH4, and N2O) emissions. Three high-rise layer houses (256,600 W-36 hens per house) received standard industry diet (Control), a diet containing 7% EcoCal (EcoCal) or a diet containing 10% DDGS (DDGS). Gaseous emissions were continuously monitored during the period of December 2007 to December 2009, covering the full production cycle. The 24-month test results revealed that mean NH3 emission rates were 0.58 +/- 0.05, 0.82 +/- 0.04, and 0.96 +/- 0.05 g/hen/day for the EcoCal, DDGS, and Control diet, respectively. Namely, compared to the Control diet, the EcoCal and DDGS diets reduced NH3 emission by an average of 39.2% and 14.3%, respectively. The concurrent H2S emission rates were 5.39 +/- 0.46, 1.91 +/- 0.13, and 1.79 +/- 0.16 mg/ hen/day for the EcoCal, DDGS, and Control diet, respectively. CO2 emission rates were similar for the three diets, 87.3 +/- 1.37, 87.4 +/- 1.26, and 89.6 +/- 1.6 g/hen/day for EcoCal, DDGS, and Control, respectively (P = 0.45). The DDGS and EcoCal houses tended to emit less CH4 than the Control house (0.16 and 0.12 vs. 0.20 g/hen/day) during the monitored summer season. The efficacy of NH3 emission reduction by the EcoCal diet decreased with increasing outside temperature, varying from 72.2% in February 2009 to -7.10% in September 2008. Manure of the EcoCal diet contained 68% higher ammonia nitrogen (NH3-N) and 4.7 times higher sulfur content than that of the Control diet. Manure pH values were 8.0, 8.9, and 9.3 for EcoCal, DDGS, and Control diets, respectively. This extensive field study verifies that dietary manipulation provides a viable means to reduce NH3 emissions from modern laying-hen houses.     

The relations between natural and civic place attachment and pro-environmental behavior

The relation between place attachment and pro-environmental behavior is unclear. Studies have reported that place attachment is associated both with more and less pro-environmental behavior. To help clarify this, we distinguished two dimensions of place attachment: civic and natural, and explored their respective influences on pro-environmental behavior. A community sample of residents (N = 104) from two proximate towns with different environmental reputations reported the strength of their civic and natural place attachment, their performance of various pro-environmental behaviors, and a number of sociodemographic characteristics. Regression analyses revealed that natural, but not civic place attachment predicted pro-environmental behavior when controlling for the town, length of residence, gender, education and age. This demonstrates that research and theory on place attachment should consider its civic and natural dimensions independently.