Properties of Pyrolytic Chars and Activated Carbons Derived from Pilot-Scale Pyrolysis of Used Tires

Abstract

Used tires were pyrolyzed in a pilot-scale quasi-inert rotary kiln. Influences of variables, such as time, temperature, and agent flow, on the activation of obtained char were subsequently investigated in a laboratory-scale fixed bed. Meso-porous pores are found to be dominant in the pore structures of raw char. Brunauer-Emmett-Teller (BET) surfaces of activated chars increased linearly with carbon burnoff. The carbon burnoff of tire char achieved by carbon dioxide (CO₂) under otherwise identical conditions was on average 75% of that achieved by steam, but their BET surfaces are almost the same. The proper activation greatly improved the aqueous adsorption of raw char, especially for small molecular adsorbates, for example, phenol from 6 to 51 mg/g. With increasing burnoff, phenol adsorption exhibited a first-stage linear increase followed by a rapid drop after 30% burnoff. Similarly, iodine adsorption first increased linearly, but it held as the burnoff exceeded 40%, which implied that the reduction of iodine adsorption due to decreasing micro-pores was partially made up by increasing mesopores. Both raw chars and activated chars showed appreciable adsorption capacity of methylene-blue comparable with that of commercial carbons. Thus, tire-derived activated carbons can be used as an excellent mesoporous adsorbent for larger molecular species.     

Vapor-Phase and Fine Particulate Matter Concentrations of Polycyclic Aromatic Hydrocarbons Measured during the Winter Months in a Northern Rocky Mountain Urban Airshed

Abstract

A fine particulate matter (PM_2.5) sampling program was conducted in Missoula, MT, to investigate both the particle and vapor phases of PM_2.5-associated polycyclic aromatic hydrocarbons (PAHs) found in a northern Rocky Mountain urban airshed. Twenty-four-hour samples were collected during the cold winter months of January through April 2002, when many of the more volatile organic components of PM_2.5 were expected to be found in the condensed particle form. To meet analytical detection limits, each of the 12 individual sample days were aggregated into four total filter and polyurethane foam (PUF) samples, respectively, with each aggregate containing 3 sample days. Quartz filter (particle-phase PAHs) and PUF (vapor-phase PAHs) aggregates were analyzed separately for 18 individual PAHs and phenolics by gas chromatography/mass spectrometry. Results showed that 87% of the PM_2.5-associated phenolics and PAHs measured in this study were found in the vapor phase. PM_2.5-associated gas/particle partition coefficients (K_p,2.5) ranged from 0 for the lighter phenolics and PAHs to ~0.1 for some of the heavier PAHs, such as fluoranthene and pyrene. Calculating K_p,2.5 for the heaviest measured PAHs was not feasible because of low or undetectable concentrations in the vapor phases of these compounds. Phenolics and two-ringed and three-ringed PAHs were found almost exclusively in the vapor phase. Four-ringed PAHs were distributed between the particle and vapor phases, with more mass measured in the vapor phase. Very little five-ringed and higher PAHs were measured from either the filter or PUF sampling medium. These results provide information on both the concentrations and different phases of PM_2.5-associated PAHs measured during the winter months in a northern Rocky Mountain urban airshed, when concentrations of PM_2.5 are generally at their highest compared with the rest of the year.     

Relative Importance of School Bus-Related Microenvironments to Children’s Pollutant Exposure

Abstract

Real‐time concentrations of black carbon, particle‐bound polycyclic aromatic hydrocarbons, nitrogen dioxide, and fine particulate counts, as well as integrated and real‐time fine particulate matter (PM_2.5) mass concentrations were measured inside school buses during long commutes on Los Angeles Unified School District bus routes, at bus stops along the routes, at the bus loading/unloading zone in front of the selected school, and at nearby urban “background” sites. Across all of the pollutants, mean concentrations during bus commutes were higher than in any other microenvironment. Mean exposures (mean concentration times time spent in a particular microenvironment) in bus commutes were between 50 and 200 times greater than those for the loading/unloading microenvironment, and 20–40 times higher than those for the bus stops, depending on the pollutant. Although the analyzed school bus commutes represented only 10% of a child’s day, on average they contributed one‐third of a child’s 24‐hr overall black carbon exposure during a school day. For species closely related to vehicle exhaust, the within‐cabin exposures were generally dominated by the effect of surrounding traffic when windows were open and by the bus’s own exhaust when windows were closed. Low‐emitting buses generally exhibited high concentrations only when traveling behind a diesel vehicle, whereas high‐emitting buses exhibited high concentrations both when following other diesel vehicles and when idling without another diesel vehicle in front of the bus. To reduce school bus commute exposures, we recommend minimizing commute times, avoiding caravanning with other school buses, using the cleanest buses for the longest bus routes, maintaining conventional diesel buses to eliminate visible emissions, and transitioning to cleaner fuels and advanced particulate control technologies as soon as possible.     

Exhaust Temperature Profiles for Application of Passive Diesel Particulate Filters to Solid Waste Collection Vehicles in California

Abstract

To reduce public exposure to diesel particulate matter (DPM), the California Air Resources Board has begun adoption of a series of rules to reduce these emissions from in-use heavy-duty vehicles. Passive diesel particulate filter (DPF) after-treatment technologies are a cost-effective method to reduce DPM emissions and have been used on a variety of vehicles worldwide. Two passive DPFs were interim-verified in California and approved federally for use in most 1994–2002 engine families for vehicles meeting min engine exhaust temperature requirements for successful filter regeneration. Some vehicles, however, may not be suited to passive DPFs because of lower engine exhaust temperatures. The purpose of this study was to determine the applicability of two types of passive DPFs to solid waste collection vehicles, the group of vehicles for which California recently mandated in-use DPM reductions. We selected 60 collection vehicles to represent the four main types of collection vehicle duty cycles—roll-offs, and front-end, rear, and side loaders—and collected second-by-second engine exhaust temperature readings for one week from each vehicle. As a group, the collection vehicles exhibited low engine exhaust temperatures, making the application of passive DPFs to these vehicles difficult. Only 35% of tested vehicles met the temperature requirements for one passive DPF, whereas 60% met the temperature requirements for the other. Engine exhaust temperatures varied by vehicle type. Side and front-end loaders met the engine exhaust temperature requirements in the greatest number of cases with ～50–90% achieving the required regeneration temperatures. Only 8–25% of the rear loader and roll-off collection vehicles met the engine exhaust temperature requirements. Solid waste collection vehicles represent a diverse fleet with a variety of duty cycles. Low engine exhaust temperatures will need to be addressed for successful use of passive DPFs in this application.     

Investigation of Nitrogen-Bearing Species in Catalytic Steam Gasification of Poultry Litter

Abstract

The production of broiler chickens has become one of the largest sectors in U.S. agriculture, and the growing demand for poultry has led to an annual production growth rate of 5%. With increased demand for poultry, litter management has become a major challenge in the agriculture industry. Although the catalytic steam gasification has been accepted as a possible and feasible method for litter management, concern has been expressed about the presence of nitrogen and phosphorus containing species in the fuel gas and/or in the final solid residue. The possible release of phosphorus as phosphine gas in the fuel gas can have an adverse impact on the environment. Similarly, possible release of ammonia from the nitrogen containing species is also not acceptable. Hence, under partial U.S. Department of Agriculture support, a study was conducted to examine the fate and the environmental impact of the nitrogen- and phosphorus-containing species released during catalytic steam gasification of poultry litter. From various preliminary tests, it was concluded that most (～100%) of the phosphorus would remain in the residue, and some (20–70%) of the nitrogen would end up as ammonia in the fuel gas. The effects of temperature, catalyst loading, and type of catalyst on ammonia liberation were studied in a muffled furnace setup at atmospheric pressure. The fraction of nitrogen released as ammonia was found to decrease with an increase in temperature during pyrolysis and steam gasification. It also decreased with an increase in catalyst loading.     

Supply Curves for Using Powder River Basin Coal to Reduce Sulfur Emissions

Abstract

Supply curves were prepared for coal-fired power plants in the contiguous United States switching to Wyoming's Powder River Basin (PRB) low-sulfur coal. Up to 625 plants, representing ～44% of the nameplate capacity of all coal-fired plants, could switch. If all switched, more than $8.8 billion additional capital would be required and the cost of electricity would increase by up to $5.9 billion per year, depending on levels of plant derating. Coal switching would result in sulfur dioxide (SO₂) emissions reduction of 4.5 million t/yr. Increase in cost of electricity would be in the range of 0.31-0.73 cents per kilowatt-hour. Average cost of S emissions reduction could be as high as $1298 per t of SO₂. Up to 367 plants, or 59% of selected plants with 32% of 44% nameplate capacity, could have marginal cost in excess of $1000 per t of SO₂. Up to 73 plants would appear to benefit from both a lowering of the annual cost and a lowering of SO₂ emissions by switching to the PRB coal.     

Comparison of Aerobic and Anaerobic Biotreatment of Municipal Solid Waste

Abstract

To increase the operating lifetime of landfills and to lower leachate treatment costs, an increasing number of municipal solid waste (MSW) landfills are being managed as either aerobic or anaerobic bioreactors. Landfill gas composition, respiration rates, and subsidence were measured for 400 days in 200-L tanks filled with fresh waste materials to compare the relative effectiveness of the two treatments. Tanks were prepared to provide the following conditions: (1) air injection and leachate recirculation (aerobic), (2) leachate recirculation (anaerobic), and (3) no treatment (anaerobic). Respiration tests on the aerobic wet tank showed a steady decrease in oxygen consumption rates from 1.3 mol/day at 20 days to 0.1 mol/day at 400 days. Aerobic wet tanks produced, on average, 6 mol of carbon dioxide (CO₂)/kg of MSW as compared with anaerobic wet tanks, which produced 2.2 mol methane/kg of MSW and 2.0 mol CO₂/kg methane. Over the test period, the aerobic tanks settled on average 35%, anaerobic tanks settled 21.7%, and the no-treatment tank settled 7.5%, equivalent to overall mass loss in the corresponding reactors. Aerobic tanks reduced stabilization time and produced negligible odor compared with anaerobic tanks, possibly because of the 2 orders of magnitude lower leachate ammonia levels in the aerobic tank. Both treatment regimes provide the opportunity for disposal and remediation of liquid waste.     

Critique of “Precipitation in Light Extinction Reconstruction” by P.A. Ryan

Abstract

The goal of the Regional Haze Rule (RHR) is to return visibility in class I areas (CIAs) to natural levels, excluding weather-related events, by 2064. Whereas visibility, the seeing of scenic vistas, is a near instantaneous and sight-path-dependent phenomenon, reasonable progress toward the RHR goal is assessed by tracking the incremental changes in 5-yr average visibility. Visibility is assessed using a haze metric estimated from 24-hr average aerosol measurements that are made at one location representative of the CIA. It is assumed that, over the 5-yr average, the aerosol loadings and relative humidity along all of the site paths are the same and can be estimated from the 24-hr measurements. It is further assumed that any time a site path may be obscured by weather (e.g., clouds and precipitation), there are other site paths within the CIA that are not. Therefore, when calculating the haze metric, sampling days are not filtered for weather conditions. This assumption was tested by examining precipitation data from multiple monitors for four CIAs. It is shown that, in general, precipitation did not concurrently occur at all monitors for a CIA, and precipitation typically occurred 3-8 hr or less in a day. In a recent paper in this journal, Ryan asserts that the haze metric should include contributions from precipitation and conducted a quantitative assessment incorrectly based on the assumption that the Optec NGN-2 nephelometer measurements include the effects of precipitation. However, these instruments are programmed to shut down during rain events, and any data logged are in error. He further assumes that precipitation occurs as often on the haziest days as the clearest days and that precipitation light scattering (bprecip) is independent of geographic location and applied an average bprecip derived for Great Smoky Mountains to diverse locations including the Grand Canyon. Both of these assumptions are shown to be in error.     

Nematode species at risk--a metric to assess pollution in soft sediments of freshwaters

Soft sediments are often highly polluted as many of the toxic chemicals introduced into surface waters bind to settling particles. The resulting accumulation of pollutants in the sediments poses a risk for benthic communities. However, pollution induced changes in benthic communities have been difficult to determine when using macro-invertebrates as bioindicators, as these organisms are often absent in soft sediment. The present study therefore examined the ability of meiofaunal organisms, specifically, nematodes, to assess the ecological status of soft sediments. Over a 9-year period, nematode communities present in sediments collected from large rivers and lake Constance in Germany were studied. These sediments showed a large range of physico-chemical properties and anthropogenic contamination. After the degree of metal and organic contamination was translated into ecotoxicologically more relevant toxic units (TUs), multivariate methods were used to classify nematode taxa in species at risk (NemaSPEAR) or not at risk (NemaSPE(not)AR). This approach clearly distinguished the influence of sediment texture from that of the toxic potential of the samples and thus allowed classification of the nematode species according to their sensitivity to or tolerance of toxic stress. Two indices, expressing the proportion of species at risk within a sample (NemaSPEAR[%](metal), NemaSPEAR[%](organic)), were calculated from independent data sets obtained in field and experimental studies and showed good correlations with the toxic potential (field data) or chemical concentrations (microcosm data). NemaSPEAR[%] indices for metal and organic pollution were therefore judged to be suitable for assessing the impact of chemical contamination of freshwater soft sediments.     

Quantifying summed fullerene nC60 and related transformation products in water using LC LTQ Orbitrap MS and application to environmental samples

The application of engineered nanomaterials increases strongly. Development of analytical techniques and their application to environmental samples is essential for human and environmental risk assessment of the nanoparticles. The objective of this study was to develop a sensitive analytical method to quantify nC(60) in water, using accurate mass screening liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. nC(60) can be transformed by oxidation, reduction and photochemical reaction. Therefore, the formation of some transformation products of nC(60) was studied as well. Finally, the developed analytical method was applied to surface water samples from several locations in the Netherlands. The developed method enabled to detect and quantify aqueous concentrations of the summed nC(60) and its transformation products as low as 5 ng/L. It was observed that nC(60) transformation products exceed quantities of the parent C(60). Despite the high sensitivity of the developed method, no nC(60) or transformation products were detected in an array of Dutch surface waters. This might be due to low emissions, losses in the aqueous phase by sedimentation, sorption or further transformation processes.