NOx Removal with Combined Selective Catalytic Reduction and Selective Noncatalytic Reduction: Pilot-Scale Test Results

Pilot-scale tests were conducted to develop a combined nitrogen oxide (NO_x) reduction technology using both selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR). A commercially available vanadium- and titanium-based composite honeycomb catalyst and enhanced urea (NH₂CONH₂) were used with a natural-gas-fired furnace at a NO_x concentration of 110 ppm. Changes in SNCR chemical injection temperature and stoichiometry led to varying levels of post-furnace ammonia (NH₃), which acts as the reductant feed to the downstream SCR catalyst. The urea-based chemical could routinely achieve SNCR plus SCR total NO_x reductions of 85 percent with less than 3 ppm NH₃ slip at reductant/NO_x stoichiometries ranging from about 1.5 to 2.5 and SCR space velocities of 18,000 to 32,000 h^?1. This pilot-scale research has shown that SNCR and SCR can be integrated to achieve high NO_x removal. SNCR provides high temperature reduction of NO_x followed by further removal of NO_x and minimization of NH₃ slip by a significantly downsized (high-space velocity) SCR.     

The effect of metal catalysts on the formation of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran precursors

The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl₂), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl₂ occurred as a result of a metal-catalyzed reaction of HCl with O₂. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

Variables affecting emissions of PCDD/Fs from uncontrolled combustion of household waste in barrels

The uncontrolled burning of household waste in barrels has recently been implicated as a major source of airborne emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). A detailed, systematic study to understand the variables affecting emissions of PCDD/Fs from burn barrels was performed. The waste composition, fullness of the barrel, and the combustion conditions within the barrel all contribute significantly to determining the emissions of PCDD/Fs from burn barrels. The study found no statistically significant effect on emissions from the Cl content of waste except at high levels, which are not representative of typical household waste. At these elevated Cl concentrations, the impact of Cl on PCDD/F emissions was found to be independent of the form of the Cl (inorganic or organic). For typical burn conditions, most of the PCDD/F emissions appear to be associated with the later stages of the burn when the waste is smoldering. Polychlorinated biphenyls (PCBs) were also measured for a subset of the tests. For the nominal waste composition, the average emissions were 76.8 ng toxic equivalency units (TEQ)WHO98/kg of waste combusted, which suggests that uncontrolled burning of household waste could be a major source of airborne PCDD/Fs in the United States.     

Mono- to tri-chlorinated dibenzodioxin (CDD) and dibenzofuran (CDF) congeners/homologues as indicators of CDD and CDF emissions from municipal waste and waste/coal combustion

Total homologue concentrations and select congener concentrations from amongst the mono- to tri-chlorinated dibenzodioxins (CDDs) and dibenzofurans (CDFs) are used to model both Total (mono- to octa-) CDD + CDF emissions and the toxicity equivalent (TEQ) of the 2,3,7,8-chlorine-substituted emissions. Analysis of emission data from two facilities indicates that use of total homologue concentrations shows limited, facility-specific correlations with Total CDDs/CDFs and TEQ. Concentrations of select mono- to tri-CDD/CDF congeners show promising correlation with CDD/CDF TEQ across facilities, suggesting that these compounds can act as TEQ indicators.     

Determination of relative assay response factors for toxic chlorinated and brominated dioxins/furans using an enzyme immunoassay (EIA) and a chemically-activated luciferase gene expression cell bioassay (CALUX)

Determination of toxic activity requires knowledge of both the concentration and toxicity to evaluate the risk for adverse human health and environmental effects. A chemically-activated luciferase gene expression cell bioassay system (CALUX) and an antibody-based method enzyme immunoassay (EIA) were used to detect the dioxin-like response of several polybrominated, polychlorinated, and polybrominated/chlorinated dibenzo-p-dioxins/furans (PBDDs/Fs, PCDDs/Fs, and PBCDDs/Fs, respectively). It has been suggested that the biological activity of the brominated and mixed bromo/chloro compounds is similar to their chlorinated analogues (measured by binding to the Ah receptor). PBDD/F, PCDD/F, and PBCDD/F laboratory standards exhibited biological activity ranging over three orders of magnitude. The highest relative potency (REP) values from CALUX analysis, when compared to 2,3,7,8-TCDD, were 2,3,7,8-TBDD at 0.99 (± 0.07), 1,2,3,7,8-PeCDD at 0.69, and 2-Br-3,7,8-TriCDD at 0.72 (± 0.02). Cross-reactivities were calculated using EIA for several PBDDs/Fs and PBCDDs. The highest percent cross-reactivity was found for 2,3,7,8-TBDD at 138 (± 34%), and 2,3,7-TriBDD at 84 (± 36%).     

Traffic and meteorological impacts on near-road air quality: summary of methods and trends from the Raleigh Near-Road Study

A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.     

Entrained-flow adsorption of mercury using activated carbon

Bench-scale experiments were conducted in a flow reactor to simulate entrained-flow capture of elemental mercury (Hg0) by activated carbon. Adsorption of Hg0 by several commercial activated carbons was examined at different C:Hg ratios (by weight) (350:1-29,000:1), particle sizes (4-44 microns), Hg0 concentrations (44, 86, and 124 ppb), and temperatures (23-250 degrees C). Increasing the C:Hg ratio from 2100:1 to 11,000:1 resulted in an increase in removal from 11 to 30% for particle sizes of 4-8 microns and a residence time of 6.5 sec. Mercury capture increased with a decrease in particle size. At 100 degrees C and an Hg0 concentration of 86 ppb, a 20% Hg0 reduction was obtained with 4- to 8-micron particles, compared with only a 7% reduction for 24- to 44-micron particles. Mercury uptake decreased with an increase in temperature over a range of 21-150 degrees C. Only a small amount of the Hg0 uptake capacity is being utilized (less than 1%) at such short residence times. Increasing the residence time over a range of 3.8-13 sec did not increase adsorption for a lignite-based carbon; however, increasing the time from 3.6 to 12 sec resulted in higher Hg0 removal for a bituminous-based carbon.     

Emission factors for PCDD/PCDF and dl-PCB from open burning of biomass

The Stockholm Convention on Persistent Organic Pollutants includes in its aims the minimisation of unintentional releases of polychlorinated dibenzo-dioxins and dibenzofurans (PCDD/PCDF) and dioxin like PCB (dl-PCB) to the environment. Development and implementation of policies to achieve this aim require accurate national inventories of releases of PCDD/PCDF/dl-PCB. To support this objective, the Conference of Parties established a process to review and update the UNEP Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. An assessment of all emission inventories was that for many countries open burning of biomass and waste was identified as the major source of PCDD/PCDF releases. However, the experimental data underpinning the release estimates used were limited in number and, consequently, confidence in the accuracy of the emissions predictions was low. There has been significant progress in measurement technology since the last edition of the Toolkit in 2005. In this paper we reassess published emission factors for release of PCDD/PCDF and dl-PCB to land and air.In total, four types of biomass and 111 emission factors were assessed. It was found that there are no systematic differences in emission factors apparent between biomass types or fire classes. The data set is best described by a lognormal distribution. The geometric mean emission factors (EFs) for releases of PCDD/PCDF to air for the four biomass classes used in the Toolkit (sugarcane, cereal crops, forest and savannah/grass) are 1.6 μg TEQ (t fuel)⁻¹, 0.49 μg TEQ (t fuel)⁻¹, 1.0 μg TEQ (t fuel)⁻¹ and 0.4 μg TEQ (t fuel)⁻¹, respectively. Corresponding EFs for release of PCDD/PCDF to land are 3.0 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹, 1.1 ng TEQ (kg ash)⁻¹ and 0.67 ng TEQ (kg ash)⁻¹. There are now also sufficient published data available to evaluate EFs for dl-PCB release to air for sugarcane, forest and grass/savannah; these are 0.03 μg TEQ (t fuel)⁻¹, 0.09 μg TEQ (t fuel)⁻¹ and 0.01 μg TEQ (t fuel)⁻¹, respectively. The average EF for dl-PCB release to land is 0.19 ng TEQ (kg ash)⁻¹. Application of these EFs to national emissions of PCDD/PCDF for global estimates from open burning will lower previous estimates of PCDD/PCDF releases to air and to land by 85% and 90%, respectively. For some countries, the ranking of their major sources will be changed and open burning of biomass will become less significant than previously concluded.     

Effects of combustion parameters on polychlorinated dibenzodioxin and dibenzofuran homologue profiles from municipal waste and coal co-combustion

Variation in polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD and PCDF) homologue profiles from a pilot scale (0.6 MW_t, 2×10⁶ Btu/h), co-fired-fuel [densified refuse derived fuel (dRDF) and high-sulfur Illinois coal] combustion system was used to provide insights into effects of combustion parameters on PCDD and PCDF pollutant formation. A 24-run, statistically designed test matrix varied dRDF and/or coal firing rates (at a constant targeted energy release rate) along with a range of process variables including calcium hydroxide injection, hydrogen chloride (HCl) concentration, flue gas temperature, quench, and residence time such that the results would be relatable to a wide variety of combustion conditions. Statistical analysis of the molar homologue profiles enabled interpretation based on non-confounding variables. A multivariate, generalized additive model, based on transformations of the design variables, described 83% of the variation of the profiles characterized by log ratios of the homologue molar concentrations. This method identifies the operating parameters that are most significant in determining the PCDD/F homologue profiles. The model can be exercised to predict homologue profiles through input of these system-specific operating parameters. For example, both higher HCl and sulfur dioxide concentrations favor higher relative formation of the lower chlorinated PCDF homologues.