Urban-Center CO Air Quality Projections

The distribution of mutagenic activity and nitroaromatic components of polycyclic organic matter (POM) in ambient air at industrial, urban, suburban, rural, and remote sites was studied using organic extracts from high volume aerosol samples. Direct-acting mutagens including 1-nitropyrene (1-NP), dinitropyrenes (DNP), and hydroxynitropyrenes (HNP) were measured by high performance liquid chromatography while the mutagenicity was determined in the Salmonella bioassay with strain TA-98. Benzo(a)pyrene (BaP), one of the possible precursors of nitroaromatic compounds in POM, was also measured. In comparing samples from a range of sites, TSP and the concentration of BaP per mass of particulate matter decreased, as expected, at greater distances from urban and industrial combustion sources. However, the concentrations of polar nitroaromatic POM compounds per mass of particles were higher at a remote site than in nonindustrial urban and suburban areas. The mutagenicity in particulate matter extracts from the remote area was predominantly (>90 percent) in the very polar fractions. There were also high atmospheric levels of nitroaromatic compounds and mutagenicity in heavily industrialized areas. These observations may reflect the influences of source emissions, atmospheric transformations of POM compounds, and ther atmospheric processes on the composition of ambient suspended particulate matter.     

Relationship between Urban and Rural Sulfate Levels

Abstract

The topic of global warming as a result of increased atmospheric CO₂ concentration is arguably the most important environmental issue that the world faces today. It is a global problem that will need to be solved on a global level. The link between anthropogenic emissions of CO₂ with increased atmospheric CO₂ levels and, in turn, with increased global temperatures has been well established and accepted by the world. International organizations such as the United Nations Framework Convention on Climate Change (UNFCCC) and the Intergovernmental Panel on Climate Change (IPCC) have been formed to address this issue. Three options are being explored to stabilize atmospheric levels of greenhouse gases (GHGs) and global temperatures without severely and negatively impacting standard of living: (1) increasing energy efficiency, (2) switching to less carbon-intensive sources of energy, and (3) carbon sequestration. To be successful, all three options must be used in concert. The third option is the subject of this review. Specifically, this review will cover the capture and geologic sequestration of CO₂ generated from large point sources, namely fossil-fuel-fired power gasification plants. Sequestration of CO₂ in geological formations is necessary to meet the President’s Global Climate Change Initiative target of an 18% reduction in GHG intensity by 2012. Further, the best strategy to stabilize the atmospheric concentration of CO₂ results from a multifaceted approach where sequestration of CO₂ into geological formations is combined with increased efficiency in electric power generation and utilization, increased conservation, increased use of lower carbonintensity fuels, and increased use of nuclear energy and renewables.

This review covers the separation and capture of CO₂ from both flue gas and fuel gas using wet scrubbing technologies, dry regenerable sorbents, membranes, cryogenics, pressure and temperature swing adsorption, and other advanced concepts. Existing commercial CO₂ capture facilities at electric power-generating stations based on the use of monoethanolamine are described, as is the Rectisol process used by Dakota Gasification to separate and capture CO₂ from a coal gasifier.

Two technologies for storage of the captured CO₂ are reviewed—sequestration in deep unmineable coalbeds with concomitant recovery of CH4 and sequestration in deep saline aquifers. Key issues for both of these techniques include estimating the potential storage capacity, the storage integrity, and the physical and chemical processes that are initiated by injecting CO₂ underground. Recent studies using computer modeling as well as laboratory and field experimentation are presented here. In addition, several projects have been initiated in which CO₂ is injected into a deep coal seam or saline aquifer. The current status of several such projects is discussed. Included is a commercial-scale project in which a million tons of CO₂ are injected annually into an aquifer under the North Sea in Norway. The review makes the case that this can all be accomplished safely with off-the-shelf technologies. However, substantial research and development must be performed to reduce the cost, decrease the risks, and increase the safety of sequestration technologies.

This review also includes discussion of possible problems related to deep injection of CO₂ . There are safety concerns that need to be addressed because of the possibilities of leakage to the surface and induced seismic activity. These issues are presented along with a case study of a similar incident in the past. It is clear that monitoring and verification of storage will be a crucial part of all geological sequestration practices so that such problems may be avoided. Available techniques include direct measurement of CO₂ and CH4 surface soil fluxes, the use of chemical tracers, and underground 4-D seismic monitoring.

Ten new hypotheses were formulated to describe what happens when CO₂ is pumped into a coal seam. These hypotheses provide significant insight into the fundamental chemical, physical, and thermodynamic phenomena that occur during coal seam sequestration of CO₂ .     

Evaluation of Selected Gaseous Halocarbons for Use in source Test Performance Audits

A repository of 38 gaseous organic compounds in compressed gas cylinders has been established by EPA. This repository was established to provide standards for source test performance audits, that is, quantitative quality assurance tests. Among these compounds are ten halogenated organic species, which are the focus of this paper.

Stability studies of all ten compounds have been performed to determine the feasibility of using them as performance audit standards. Results indicate that all of the halocarbons tested are adequately stable to be used as reliable audit standards.

Subsequent to completion of stability studies, four of the ten halocarbons were used in source test performance audits. Results are available at this time for two of the four compounds; the results show agreement within 10% of the concentrations previously established by Research Triangle Institute.     

Trends and Relationships of O3, NOx and HC in the South Coast Air Basin of California

A basin-wide air quality trend analysis for the South Coast Air Basin of California is conducted for hydrocarbons (HC), NO_x, O₃ and CO using multi-station composite daily maximum-hour average ambient concentrations for the third quarter (July, August and September) from 1968 to 1985. Emissions and air quality trends are compared for the period 1968-1984. Ambient HC and NOX trends are somewhat different from estimated emission trends of HC and NO_x, while a definite, downward trend of ambient CO is consistent with vehicular emission control measures. Basin-wide ambient HC, NO_x and O₃ appear to show downward trends for the period 1970-1985, but because of high fluctuations it is difficult to delineate trends for shorter periods. The meteorology (850 mb temperature)-adjusted O₃ shows a more consistent downward trend than does unadjusted O₃. Polynomial and multiplicative regression models for basin-wide empirical O₃-HC-NO_x relationships Indicate that the O₃ variation is explained largely by the meteorological variable (850 mb temperature) although model estimations are improved by adding HC and NO_x concentration terms.     

Effect of Moisture on the Pollutant Concentration Measurement

The effects of removing moisture from gaseous samples on the measurement of pollutant concentration were studied. Simple mathematical analysis was conducted to derive the formula for correcting the measured results. It was found that the error increases with increase in relative humidity or increase in temperature. The error may become significant under extreme conditions.     

An Analysis of Biomedical Waste Incineration

The California Air Resources Board (ARB) completed a series of source tests of eight operating biomedical waste incinerators (BMWI) under conditions of typical operation. The emissions of certain metals, and chlorinated dioxins and furans in the flue gases of BMWI are relatively high in comparison to emissions from other combustion sources, such as hazardous waste or municipal waste incinerators of modern design. This study reports on an analysis of the status of the existing regulatory framework and the California data base. Clarification of definitional issues at the federal level is needed to effectively treat BMWI management issues. Although few relationships among combustion parameters and emissions were uncovered, patterns of emissions were evident, suggesting commonality and relationships among the waste stream constituents and emissions. Potential implications for future research, operation of BMWI, controls and source reduction and waste segregation strategies are also discussed.     

An Intelligent Emissions Controller for Fuel Lean Gas Reburn in Coal-Fired Power Plants

ABSTRACT

The application of artificial intelligence techniques for performance optimization of the fuel lean gas reburn (FLGR) system is investigated. A multilayer, feedforward artificial neural network is applied to model static nonlinear relationships between the distribution of injected natural gas into the upper region of the furnace of a coal-fired boiler and the corresponding oxides of nitrogen (NO_x) emissions exiting the furnace. Based on this model, optimal distributions of injected gas are determined such that the largest NO_x reduction is achieved for each value of total injected gas. This optimization is accomplished through the development of a new optimization method based on neural networks. This new optimal control algorithm, which can be used as an alternative generic tool for solving multidimensional nonlinear constrained optimization problems, is described and its results are successfully validated against an off-the-shelf tool for solving mathematical programming problems. Encouraging results obtained using plant data from one of Commonwealth Edison's coal-fired electric power plants demonstrate the feasibility of the overall approach.

Preliminary results show that the use of this intelligent controller will also enable the determination of the most cost-effective operating conditions of the FLGR system by considering, along with the optimal distribution of the injected gas, the cost differential between natural gas and coal and the open-market price of NO_x emission credits. Further study, however, is necessary, including the construction of a more comprehensive database, needed to develop high-fidelity process models and to add carbon monoxide (CO) emissions to the model of the gas reburn system.     

Investigation of the Potential Antimicrobial Efficacy of Sealants Used in HVAC Systems

ABSTRACT

Recent experiments confirm field experience that duct cleaning alone may not provide adequate protection from regrowth of fungal contamination on fiberglass duct liner (FGDL). Current recommendations for remediation of fungally contaminated fiberglass duct materials specify complete removal of the materials. But removal of contaminated materials can be extremely expensive. Therefore, a common practice in the duct-cleaning industry is the postcleaning use of antimicrobial surface coatings with the implication that they may contain or limit regrowth.

Little information is available on the efficacy of these treatments. This paper describes a study to evaluate whether three commercially available antimicrobial coatings, placed on a cleaned surface that 1 year previously had been actively growing microorganisms, would be able to prevent regrowth. The three coatings contained different active antimicrobial compounds. All three of the coatings were designed for use on heating, ventilation, and air conditioning (HVAC) system components or interior surfaces of lined and unlined duct systems. Coating I was a polyacrylate copolymer containing zinc oxide and borates. Coating II was an acrylic coating containing decabromodiphenyl oxide and antimony trioxide. Coating III was an acrylic primer containing a phosphated quaternary amine complex.

The study included field and laboratory assessments. The three treatments were evaluated in an uncontrolled field setting in an actual duct system. The laboratory study broadened the field study to include a range of humidities under controlled conditions. Both static and dynamic chamber laboratory experiments were performed. The results showed that two of the three antimicrobial coatings limited the regrowth of fungal contamination, at least in the short term (the 3-month time span of the study); the third did not. Before use in the field, testing of the efficacy of antimicrobial coatings under realistic use conditions is recommended because antimicrobials have different baseline activities and interact differently with the substrate that contains them and their local environment.     

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.     

Cs, Pu concentrations and the Pu/Pu atom ratio in a sediment core from the sub-aqueous delta of Yangtze River estuary

A sediment core collected from the sub-aqueous delta of the Yangtze River estuary was subjected to analyses of ¹³⁷Cs and plutonium (Pu) isotopes. The ¹³⁷Cs was measured using γ-spectrometry at the laboratories at the Nanjing University and Pu isotopes were determined with Accelerator Mass Spectrometry (AMS), measurements made at the Australian National University. The results show considerable structure in the depth concentration profiles of the ¹³⁷Cs and ^239+240Pu. The shape of the vertical ¹³⁷Cs distribution in the sediment core was similar to that of the Pu. The maximum ¹³⁷Cs and ^239+240Pu concentrations were 16.21 ± 0.95 mBq/g and 0.716 ± 0.030 mBq/g, respectively, and appear at same depth. The average ²⁴⁰Pu/²³⁹Pu atom ratio was 0.238 ± 0.007 in the sediment core, slightly higher than the average global fallout value. The changes in the ²⁴⁰Pu/²³⁹Pu atom ratios in the sediment core indicate the presence of at least two different Pu sources, i.e., global fallout and another source, most likely close-in fallout from the Pacific Proving Grounds (PPG) in the Marshall Islands, and suggest the possibility that Pu isotopes are useful as a geochronological tool for coastal sediment studies. The ¹³⁷Cs and ^239+240Pu inventories were estimated to be 7100 ± 1200 Bq/m² and 407 ± 27 Bq/m², respectively. Approximately 40% of the ^239+240Pu inventory originated from the PPG close-in fallout and about 50% has derived from land-origin global fallout transported to the estuary by the river. This study confirms that AMS is a useful tool to measure ²⁴⁰Pu/²³⁹Pu atom ratio and can provide valuable information on sedimentary processes in the coastal environment.