Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.     

Responses of Gammarus pulex (Amphipoda, Crustacea) to metalliferous effluents: identification of toxic components and the importance of interpopulation variation

This study was designed to evaluate the ability of an in-situ bioassay to assess the impact of complex effluents on freshwaters and to identify toxic components. Reductions in the feeding rate of Gammarus pulex proved to be a sensitive indicator of the impact of metalliferous effluents on receiving water quality. The effluents contained a mixture of five potentially toxic metals. By combining information on feeding rates with bioaccumulation data, two metals, iron and manganese, were identified as the probable toxic agents. Laboratory experiments validated the conclusions reached from the field study and confirmed that iron was a major toxicant. The sensitivities of Gammarus pulex from a metal-contaminated site and a clean site were compared during both the field and laboratory studies. Interpopulation differences in the response of G. pulex to toxicants were detected in the field study but not in the laboratory experiments. Possible reasons for this are discussed.     

Accumulation of metals,trace elements and semi-volatile organic compounds on exterior window surfaces in Baltimore

Organic films have been found to develop on window surfaces [Diamond et al., Environmental Science and Technology 34 (2000a) 2900]. The film contains organic compounds that are in dynamic equilibrium with the gas-phase in air, and organic and inorganic compounds and elements associated with deposited air particles. In this study, the exterior surfaces of windows were sampled in downtown and suburban Baltimore, Maryland. Higher concentrations of PCBs, PAH, metals and trace elements were found at downtown than a suburban site. PCBs in the films at downtown sites were dominated by penta and hexa homologue groups and PAH signatures resembled that of vehicle emissions. Twenty-six metals and trace elements were separated into two groups according to their enrichment factors (EF). Ag, Hg, Se, Sb and Zn had EF > 100, suggesting anthropogenic sources of these metals in the films; whereas Fe, Ca, Co, Cr and others had EF <10, suggesting a crustal origin. An unusual profile dominated by deca- and nona- PCBs and relatively higher concentrations of Ag, Hg and Zn may be attributable to emissions from a medical waste incinerator. Dry deposition fluxes of selected metals on windows were 1.4-94 times higher on windows with than without films, indicating that the film increases the dry deposition of particles and their associated chemicals. This implies that film development, which is associated with elevated VOC and SOC emissions to urban air, will increase film development that will, in turn, increase the accumulation of other atmospherically deposited constituents such as metals.     

Two Decades of Experimental Manipulations of Heaths and Forest Understory in the Subarctic

Current atmospheric warming due to increase of greenhouse gases will have severe consequences for the structure and functioning of arctic ecosystems with changes that, in turn, may feed back on the global-scale composition of the atmosphere. During more than two decades, environmental controls on biological and biogeochemical processes and possible atmospheric feedbacks have been intensely investigated at Abisko, Sweden, by long-term ecosystem manipulations. The research has addressed questions like environmental regulation of plant and microbial community structure and biomass, carbon and nutrient pools and element cycling, including exchange of greenhouse gases and volatile organic compounds, with focus on fundamental processes in the interface between plants, soil and root-associated and free-living soil microorganisms. The ultimate goal has been to infer from these multi-decadal experiments how subarctic and arctic ecosystems will respond to likely environmental changes in the future. Here we give an overview of some of the experiments and main results.     

Two decades of experimental manipulations of heaths and forest understory in the subarctic

Current atmospheric warming due to increase of greenhouse gases will have severe consequences for the structure and functioning of arctic ecosystems with changes that, in turn, may feed back on the global-scale composition of the atmosphere. During more than two decades, environmental controls on biological and biogeochemical processes and possible atmospheric feedbacks have been intensely investigated at Abisko, Sweden, by long-term ecosystem manipulations. The research has addressed questions like environmental regulation of plant and microbial community structure and biomass, carbon and nutrient pools and element cycling, including exchange of greenhouse gases and volatile organic compounds, with focus on fundamental processes in the interface between plants, soil and root-associated and free-living soil microorganisms. The ultimate goal has been to infer from these multi-decadal experiments how subarctic and arctic ecosystems will respond to likely environmental changes in the future. Here we give an overview of some of the experiments and main results.     

Atmospheric fall-out of metals around the Murano glass-making district (Venice,Italy)

Background, aim and scope  

Murano’s glass-makers have held a monopoly on quality glass-making for centuries known all over the world. Artistic glass manufacture entails exposure to complex mixtures of pollutants, including metals. A few studies have reported high levels of trace elements in marine waters, sediments and mussels around Murano and shown that emissions from Murano glass-making workshops significantly influence air quality in the Venice area. Nevertheless, to date, there is very little information on atmospheric concentrations and virtually none on atmospheric deposition fluxes of trace elements around the island. This study presents data on the distribution of trace elements in the air and atmospheric depositions around Murano, based on a 2-year sampling period.     

Investigation of Selective Catalytic Reduction Impact on Mercury Speciation under Simulated NOx Emission Control Conditions

Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NO_x) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NO_x reduction, promote the formation of oxidized mercury (Hg²⁺).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg⁰) oxidation. Bench-scale experiments were conducted to investigate Hg⁰ oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO₂) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO₂ in the flue gases on Hg⁰ oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg⁰ to Hg²⁺ under SCR reaction conditions. The importance of HCl for Hg⁰ oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg⁰ oxidation occurring across the SCR reactors in the field.     

Atmospheric dispersion in the presence of a three-dimensional cubical obstacle: Modelling of mean concentration and concentration fluctuations

This paper presents computational simulations of atmospheric dispersion experiments conducted around isolated obstacles in the field. The computational tool used for the simulations was the code ADREA-HF, which was especially developed for the simulation of the dispersion of positively or negatively buoyant gases in complicated geometries. The field experiments simulated involve a single cubic obstacle normal to the mean wind direction and two upwind sources of ammonia and propane, with the ammonia source located at different lateral positions [Mavroidis, I., Griffiths, R.F., Hall, D.J., 2003. Field and wind tunnel investigations of plume dispersion around single surface obstacles. Atmospheric Environment 37, 2903–2918]. Concentrations and concentration fluctuations for both gases were calculated by the model and compared with the experimental results. Certain modelling aspects were studied, such as the effect of using different turbulence closure schemes in the computations. Furthermore, specific characteristics of dispersion were investigated using the computational tool, such as the effect of the lateral displacement of a source on the concentration fluctuations intensity, the effects of natural variability and the sensitivity of concentrations to wind direction fluctuations. The results showed a good level of agreement between calculated and measured concentrations and concentration fluctuations when ensemble averaged data were available from the field experiments. Differences observed between measured and predicted concentrations and concentration fluctuations, in the case of laterally displaced sources, were mainly attributed to the specificities of the experimental cases, such as the interaction of a laterally displaced plume with an obstacle, and to the variability observed in the field. The effect of this variability is indicated by the difference between the predicted-to-observed ratios of ensemble-averaged centreline values for propane and the respective ratios from the single ammonia experiment with co-located gas sources, the latter being higher by upto 30% for concentrations and 70% for concentration fluctuations. Using the computational tool it was shown that, for a laterally displaced source, a change of 5° in the mean wind direction can lead up to a 100% variation in the measured concentrations.     

UraniumVI sorption behavior on silicate mineral mixtures

UraniumVI sorption experiments involving quartz and clinoptilolite, important mineral phases at the proposed US nuclear waste repository at Yucca Mountain, NV, were conducted to evaluate the ability of surface complexation models to predict UVI sorption onto mineral mixtures based on parameters derived from single-mineral experiments. The experiments were conducted at an initial UVI aqueous concentration of approximately 2.0 x 10(-7) mol.l-1 (0.1 mol.l-1 NaNO3 matrix) and over the pH range approximately 2.5 to approximately 9.5. The UVI solutions were reacted with either quartz or clinoptilolite only, or with mixtures of the two minerals. The experiments were carried out under atmospheric pCO2(g) conditions (in loosely capped containers) or under limited pCO2(g) (in capped containers or in a glove box). Data from sorption experiments on quartz at atmospheric pCO2 conditions were used to derive UVI binding constants for a diffuse-layer surface complexation model (DLM). The DLM was then used with surface area as a scaling factor to predict sorption of UVI onto clinoptilolite and clinoptilolite/quartz mixtures under both atmospheric and low pCO2 conditions. The calculations reproduced many aspects of the pH-dependent sorption behavior. If this approach can be demonstrated for natural mineral assemblages, it may be useful as a relatively simple method for improving radionuclide transport models in performance-assessment calculations.     

Comparison of particle size distributions and elemental partitioning from the combustion of pulverized coal and residual fuel oil

U.S. Environmental Protection Agency (EPA) research examining the characteristics of primary PM generated by the combustion of fossil fuels is being conducted in efforts to help determine mechanisms controlling associated adverse health effects. Transition metals are of particular interest, due to the results of studies that have shown cardiopulmonary damage associated with exposure to these elements and their presence in coal and residual fuel oils. Further, elemental speciation may influence this toxicity, as some species are significantly more water-soluble, and potentially more bio-available, than others. This paper presents results of experimental efforts in which three coals and a residual fuel oil were combusted in three different systems simulating process and utility boilers. Particle size distributions (PSDs) were determined using atmospheric and low-pressure impaction as well as electrical mobility, time-of-flight, and light-scattering techniques. Size-classified PM samples from this study are also being utilized by colleagues for animal instillation experiments. Experimental results on the mass and compositions of particles between 0.03 and > 20 microns in aerodynamic diameter show that PM from the combustion of these fuels produces distinctive bimodal and trimodal PSDs, with a fine mode dominated by vaporization, nucleation, and growth processes. Depending on the fuel and combustion equipment, the coarse mode is composed primarily of unburned carbon char and associated inherent trace elements (fuel oil) and fragments of inorganic (largely calcium-alumino-silicate) fly ash including trace elements (coal). The three coals also produced a central mode between 0.8- and 2.0-micron aerodynamic diameter. However, the origins of these particles are less clear because vapor-to-particle growth processes are unlikely to produce particles this large. Possible mechanisms include the liberation of micron-scale mineral inclusions during char fragmentation and burnout and indicates that refractory transition metals can contribute to PM < 2.5 microns without passing through a vapor phase. When burned most efficiently, the residual fuel oil produces a PSD composed almost exclusively of an ultrafine mode (approximately 0.1 micron). The transition metals associated with these emissions are composed of water-soluble metal sulfates. In contrast, the transition metals associated with coal combustion are not significantly enriched in PM < 2.5 microns and are significantly less soluble, likely because of their association with the mineral constituents. These results may have implications regarding health effects associated with exposure to these particles.     

Polybrominated diphenyl ethers in various atmospheric environments of Taiwan: their levels, source identification and influence of combustion sources

In this study, ambient air samples from different atmospheric environments were examined for both PBDE and PCDD/F characteristics to verify that combustion is a significant PBDE emission source. The mean ± SD atmospheric PBDE concentrations were 165 ± 65.0 pg Nm⁻³ in the heavy steel complex area and 93.9 ± 24.5 pg Nm⁻³ in the metals complex areas, 4.7 and 2.7 times higher than that (35.3 ± 15.5 pg Nm⁻³) in the urban areas, respectively. The statistically high correlation (r = 0.871, p < 0.001) found between the atmospheric PBDE and PCDD/F concentrations reveals that the combustion sources are the most likely PBDE emission sources. Correspondence analysis shows the atmospheric PBDEs of the heavy steel and metals complex areas are associated with BDE-209, -203, -207, -208, indicative of combustion source contributions. Furthermore, the PBDEs in urban ambient air experience the influence of the evaporative releases of the commercial penta- and octa-BDE mixtures, as well as combustion source emissions. By comparing the PBDE homologues of indoor air, urban ambient air, and stack flue gases of combustion sources, we found that the lighter brominated PBDEs in urban ambient air were contributed by the indoor air, while their highly brominated ones were from the combustion sources, such as vehicles. The developed source identification measure can be used to clarify possible PBDE sources not only for Taiwanese atmosphere but also for other environmental media in other countries associated with various emission sources in the future.     

Effects of pH on the toxicity of cadmium, copper, lead and zinc to Folsomia candida Willem, 1902 (Collembola) in a standard laboratory test system

EC₅₀s for cadmium, copper, lead and zinc were determined for juvenile production of Folsomia candida at pH6.0, 5.0 and 4.5 in a standard laboratory test system. In contrast to most previous studies where metal toxicity was increased at low pHs, in our experiments there was no clear relationship between soil acidity and EC_{50-reproduction} in this species. The EC_{50-reproduction} values (μg g⁻¹) for cadmium and zinc were similar at all three pHs (pH6.0: Cd 590, Zn 900; pH5.0: Cd 780, Zn 600; pH4.5: Cd 480, Zn 590). In contaminated field sites adjacent to primary zinc smelters, zinc is invariably present in soils at concentrations of at least 50 times that of cadmium Thus deleterious effects of mixtures of these metals on populations of Collembola in such sites can be attributed to zinc rather than cadmium.     

MEAD: an interdisciplinary study of the marine effects of atmospheric deposition in the Kattegat

This paper summarises the results of the EU funded MEAD project, an interdisciplinary study of the effects of atmospheric nitrogen deposition on the Kattegat Sea between Denmark and Sweden. The study considers emissions of reactive nitrogen gases, their transport, transformations, deposition and effects on algal growth together with management options to reduce these effects. We conclude that atmospheric deposition is an important source of fixed nitrogen to the region particularly in summer, when nitrogen is the limiting nutrient for phytoplankton growth, and contributes to the overall eutrophication pressures in this region. However, we also conclude that it is unlikely that atmospheric deposition can, on its own, induce algal blooms in this region. A reduction of atmospheric nitrogen loads to this region will require strategies to reduce emissions of ammonia from local agriculture and Europe wide reductions in nitrous oxide emissions.     

Direct GLC Coulometric Analysis of Kraft Mill Gases

A new bromine, microcoulometric titration cell has been used with a commercially-available microcoulometer for the detection and analysis of sulfur-containing gases in various kraft mill emissions. Separation of the constituents of the gaseous mixtures emitted from mill sources including the recovery furnace, digestors, evaporators, lime kiln, and dissolvers was accomplished on an 8-ft, 3/16 in. stainless steel column packed with 10% Triton X-305 on 60–80 mesh Chromosorb G, DMCS-treated. The column was isothermally operated at 30°C for 4–6 mins and then rapidly raised to 70°C The exact program was varied with the type of sample analyzed. Each source gas was initially screened by direct injection of 0.01–0.1 ml of gas to determine whether or not disproportionately large concentrations of one or more components were present. Appropriate sample volumes were then selected to provide “on-scale” recorder peaks for the major constituents. Elution times for the major constituents were observed so that these compounds could be vented at the proper time following injection of large sample volumes (up to 10 ml) for detection and analysis of minor constituents. Venting of the high concentration compounds was necessary when analyzing large volume samples to maintain near equilibrium titration conditions in the microtitration cell.     

A Transition-Flow Reactor Tube for Measuring Trace Gas Concentrations

Dry deposition contributes significantly to the acidification of ecosystems. However, difficulties in measuring dry deposition of reactive gases and fine particles make routine direct monitoring impractical. An alternate approach is to use the “concentration monitoring” method in which dry deposition flux is estimated as the product of measured concentration and estimated deposition velocity. A sampling system that performs over the period of 6 hours to 7 days, depending on atmospheric concentrations, has been developed. It consists of a Teflon cyclone to exclude particles larger than about 2 μm, selective solid adsorption media for reactive gases—some of which are sampled from a transition flow to avoid possible bias from particle evaporation, a particle filter, and a final gas adsorption filter to collect the remaining trace gas. The sampler Is the first reported application of transition flow mass transfer for the collection and quantitative measurement of trace atmospheric gases. Laboratory and field tests have shown that the sampler performs well for HNO₃(g).     

Relationship between epiphytic lichens, trace elements and gaseous atmospheric pollutants

A study was conducted to determine the joint effect of gaseous atmospheric pollutants and trace elements on epiphytic lichens. We used our data to test the hypothesis that lichens are generally insensitive to toxic effects of trace elements, and can therefore be used as accumulator organisms to estimate concentrations of these elements in the environment. In a field study in The Netherlands the abundance of epiphytic lichen species was estimated, and their supporting bark was collected. Concentrations of a range of trace elements were determined in the bark, and concentrations of atmospheric trace gases were estimated at the sites of collection. Multivariate statistics were used to determine the relation between the abundance of the species and pollutant concentrations. Atmospheric SO2 and NO2 appeared to be the most important factors determining lichen biodiversity. Nearly all species were sensitive to these compounds. The effect of the other trace elements was very slight; only Sb had a significantly negative effect on the abundance of a few species. It is concluded that lichens can safely be used as accumulator organisms in pollution studies, provided that concentration in lichen thalli reflect atmospheric concentrations.     

Field and laboratory simulations of storm water pulses: behavioural avoidance by marine epifauna

Epifaunal communities associated with macroalgae were exposed to storm water pulses using a custom made irrigation system. Treatments included Millipore freshwater, freshwater spiked with trace metals and seawater controls to allow for the relative importance of freshwater inundation, trace metals and increased flow to be determined. Experimental pulses created conditions similar to those that occur following real storm water events. Brief storm water pulses reduced the abundance of amphipods and gastropods. Freshwater was the causative agent as there were no additional effects of trace metals on the assemblages. Laboratory assays indicated that neither direct nor latent mortality was likely following experimental pulses and that epifauna readily avoid storm water. Indirect effects upon epifauna through salinity-induced changes to algal habitats were not found in field recolonisation experiments. Results demonstrate the importance of examining the effects of pulsed contaminants under realistic exposure conditions and the need to consider ecologically relevant endpoints.     

Effects of enhanced O3 and CO2 enrichment on plant characteristics in wheat and corn

The effects of CO(2) enrichment and O(3) induced stress on wheat (Triticum aestivum L.) and corn (Zea mays L.) were studied in field experiments using open-top chambers to simulate the atmospheric concentrations of these two gases that are predicted to occur during the coming century. The experiments were conducted at Beltsville, MD, during 1991 (wheat and corn) and 1992 (wheat). Crops were grown under charcoal filtered (CF) air or ambient air + 40 nl liter(-1) O(3) (7 h per day, 5 days per week) having ambient CO(2) concentration (350 microl liter(-1) CO(2)) or + 150 microl liter(-1) CO(2) (12 h per day.). Averaged over O(3) treatments, the CO(2)-enriched environment had a positive effect on wheat grain yield (26% in 1991 and 15% in 1992) and dry biomass (15% in 1991 and 9% in 1992). Averaged over CO(2) treatments, high O(3) exposure had a negative impact on wheat grain yield (-15% in 1991 and -11% in 1992) and dry biomass (-11% in 1991 and -9% in 1992). Averaged over CO(2) treatments, high O(3) exposure decreased corn grain yield by 9%. No significant interactive effects were observed for either crop. The results indicated that CO(2) enrichment had a beneficial effect in wheat (C(3) crop) but not in corn (C(4) crop). It is likely that the O(3)-induced stress will be diminished under increased atmospheric CO(2) concentrations; however, maximal benefits in crop production in wheat in response to CO(2) enrichment will not be materialized under concomitant increases in tropospheric O(3) concentration.     

The Influence of Flame-Generated Free Radicals on the Thermal Oxidation of Waste Gases

Studies of the thermal oxidation of waste gases were carried out in two variants. During the first, the destruction of waste gases was facilitated by hydrogen flame-generated radicals. During the other variant, this flame was not used, but the same temperature was maintained as in the first one. The waste gases used were mixtures of toluene with air and methane with air of 200 and 400 ppm concentrations, respectively. The experiments were performed in a flow reactor within the temperature range of 800 to 1330 K. The efficiency of oxidation of methane and toluene obtained during the first variant was considerably higher than that obtained in the second one. This was due to the promotional effect of the hydrogen flame.     

Fate of nickel in a lime-stabilized biosolid,a calcareous soil and soil–biosolid mixtures

Soil contamination with anthropogenic metals resulting from biosolid application is widespread around the world. To better predict the environmental fate and mobility of contaminants, it is critical to study the capacity of biosolid-amended soils to retain and release metals. In this paper, nickel adsorption onto a calcareous soil, a lime-stabilized biosolid, and soil–biosolid mixtures (30, 75, and 150 t biosolid/ha) was studied in batch experiments. Sorption experiments showed that (1) Ni adsorption was higher onto the biosolid than the calcareous soil, and (2) biosolid acted as an adsorbent in the biosolid–soil mixtures by increasing Ni retention capacity. The sorption tests were complemented with the estimation of Ni adsorption reversibility by successive applications of extraction solutions with water, calcium (100 mg/L), and oxalic acid (equivalent to 100 mg carbon/L). It has been shown that Ni desorption rates in soil and biosolid-amended soils were lower than 30 % whatever the chemical reagent, indicating that Ni was strongly adsorbed on the different systems. This adsorption/desorption hysteresis effect was particularly significant at the highest biosolid concentration (150 t/ha). Finally, an adsorption empirical model was used to estimate the maximum permissible biosolid application rate using French national guideline. It has been shown that desorption effects should be quantitatively considered to estimate relevant biosolid loadings.