Workshop on Primary Sulfate Emissions

This article is a summary report on a workshop, Measurement Technology and Characterization of Primary Sulfur Oxides Emission from Combustion Sources, sponsored by the EPA Environmental Sciences Research Laboratory at Research Triangle Park, NC, held in Southern Pines, NC. The objectives of the workshop were: to review and discuss current measurement methods and problem areas for sulfur oxides emission with attention focused on sulfuric acid, sulfates, and sulfur-bearing particulate matter; to review and discuss emission data from various combustion sources operating under different conditions, which include various pollutant controls, fuel composition, excess boiler oxygen, etc.; to delineate and recommend areas in need of research and development effort. Scientists were invited to present the results of their studies on primary sulfate emissions. The 3-day workshop devoted one day to measurement technology, a second to characterization, and a third to critical assessment of the presented papers and development of summary working group reports on each half-day session of the initial 2 days. Thirty-one papers were presented by 29 participants on measurements and characterization. Four working group reports were developed and summarized in the last day. Highlights of the papers and reports are briefly reviewed. Workshop proceedings are available as an EPA publication.     

experience of the forest products industry in obtaining air quality permits for new and modified sources

A detailed study of the air quality permitting process for 65 different forest products industry projects requiring preconstruction permit approvals from EPA, state, and local air pollution control agencies was conducted. The projects included a wide array of sources including kraft recovery furnaces, lime kilns, fossil fuel and wood residue fired boilers, solid wood products manufacturing facilities, paper coaters, and printing presses. Information concerning the time involved in the permitting process, costs associated with obtaining the permits, use of air quality models and ambient monitoring data, emission control technology determinations, problem areas encountered during the permitting process, perceived benefits and drawbacks of the permitting process, and the effect of permitting requirements on project planning was obtained.

The results indicate that certain permitting requirements such as Best Available Control Technology (BACT) determinations, dispersion modeling results, and use of ambient air quality monitoring data seldom influence the emission limitations ultimately imposed in the final approved permit, with 87% of the final emission limits equivalent to the applicable New Source Performance Standard (NSPS). The 65 permitting case histories also show that obtaining permits for projects subject to Prevention of Significant Deterioration (PSD) requirements takes approximately twice as long and costs twice as much as obtaining permits for projects not subject to PSD requirements.     

Testing and Commercialization of Byproduct Dibasic cids as Buffer Additives for Limestone Flue Gas esulfurization Systems

Pilot plant (0.1 MW) tests and utility boiler full scale demonstration (194 MW) of byproduct organic dibasic acids (DBA) as buffer additives to limestone scrubbers have shown performance improvements equivalent to those achieved by the addition of pure adipic acid. Both SO₂ removal efficiency and limestone utilization increased, and no significant operating problems were observed with three of the four DBA tested. Chemical and biological evaluations of scrubber samples taken during the DBA testing indicated no detectable tOxicity or mutagenicity, and no significant environmental impact is expected as a result of DBA addition. Economic estimates indicate that substitution of DBA for pure adipic acid as a buffer additive will result in additive cost savings of 30 % or greater.     

Association of benzo(a)pyrene with dissolved organic matter: Prediction of Kdom from structural and chemical properties of the organic matter

The affinity of dissolved organic matter (DOM) for binding a polycyclic aromatic hydrocarbon, benzo(a)pyrene (BaP), was measured for 11 surface and ground waters and a commercial humic acid. The hydrophobic-acid (HbA) and hydrophobic-neutral (HbN) compositions of the DOM, solution absorptivity at 270nm (ABS₂₇₀), and DOM molar volumes were determined. Waters enriched in HbA material had a larger molar volume and higher aromatic content (as indicated by the ABS₂₇₀). There was a good correlation between the size and HbA content of the DOM from the different sources and the K_dom for binding BaP. An excellent predictive relationship (r² = 0.9) was demonstrated between the ABS₂₇₀ of a water and the K_dom for binding BaP. Based on these results, it is suggested that binding of BaP to DOM depends not only on the hydrophobicity of DOM, but also on the existence of an open structure within the DOM to provide access of the aqueous solute to hydrophobic domains within the DOM.     

Exposure to polychlorinated biphenyls from an overheated transformer

A Polychlorinated Biphenyl (PCB) containing transformer released approximately 50 gallons of askarel oil. No polychlorinated dibenzofurans (PCDF) or polychlorinated dibenzodioxins (PCDD) were detected in a sample of the askarel (analytical limit of detection of 40 parts per billion per isomer group). Skin irritation, unusual tiredness, and headaches occurred in approximately 20% of the individuals at the scene of the incident. Serum PCB levels, and mean values for blood and urine tests were within normal ranges.     

Characterization of trace organic contaminants in marine sediment from Yeongil Bay, Korea: 2. Dioxin-like and estrogenic activities

This study employed mechanism-specific in vitro bioassays to help characterize the occurrence and distribution of dioxin-like and estrogenic contaminants in sediment from Yeongil Bay, Korea. Approximately 85% of the sediments tested induced significant dioxin-like activity in the H4IIE-luc bioassay, while approximately 50% induced significant estrogenic activity in the MVLN bioassay. Instrumentally-derived estimates of 2,3,7,8-tetrachlorodibenzo-p-dioxin and 17beta-estradiol equivalents tended to underestimate the magnitude of response observed in the bioassays, suggesting that compounds detected by chemical analysis did not account for all the activity associated with Yeongil Bay sediments, or that non-additive interactions were occurring. The greatest dioxin-like and estrogenic activity was associated with the mid-polarity Florisil fractions (F2) expected to contain polycyclic aromatic hydrocarbons (PAHs) as well as chlorinated dioxins and furans. As in previous studies of Korean coastal sediment, more polar fractions (F3) generated more modest responses both in terms of magnitude and the number of samples responding.     

Pesticides and metabolites in cassava, eucalyptus, plum and cashew leaves and roots in relation to a point source in Kibaha, Tanzania

Leaves of Eucalyptus sp., Prunus domestica (plum), and Anacardium occidentale (cashew), as well as roots and leaves of Manihot esculenta (cassava) were used to study the local distribution of pesticides and metabolites from a point source, an old storage site at Vikuge farm in Tanzania. The GPC-cleaned extracts were analyzed by GC-ECD and GC/MS. Eleven organochlorine pesticide residues namely pentachloroanisole, p,p'-DDT, o,p'-DDT, p,p'-DDE, o,p'-DDE, p,p'-DDD, o,p'-DDD, alpha-HCH, beta-HCH, delta-HCH and epsilon-HCH were detected in the samples. The concentrations of total DDT were 818 ng/g fw in Eucalyptus sp., 16 ng/g fw in A. occidentale and 4 ng/g fw in P. domestica. In M. esculenta, total DDT ranged from 191 to 586 ng/g fw in roots and 7 to 425 ng/g fw in leaves. The concentrations of total HCH were up to 15 ng/g fw in Eucalyptus sp., while the concentrations of pentachloroanisole were up to 2 ng/g fw in leaves of M. esculenta. There are very strong positive correlations in the concentrations of the detected compounds, suggesting that they have a common source. The low DDE/DDT ratios (0.02-0.07) in all samples indicate input of non-degraded DDT from the source. The high alpha-HCH/gamma-HCH ratios in some samples (>3.1-10) indicate input of technical HCH. The concentrations of total DDT in cassava roots were either very close to, or greater than, the FAO/WHO limit, indicating risks and concern to public health.     

Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

This paper is particularly related to elemental mercury (Hg0) oxidation and divalent mercury (Hg2+) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO2). As a powerful oxidant and chlorinating reagent, Cl2 has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO2, NO, as well as H2O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO2 and NO on Hg0 oxidation and Hg2+ reduction with the intent of unraveling unrecognized interactions among Cl species, SO2, and NO most importantly in the presence of H2O. The experimental results demonstrated that SO2 and NO had pronounced inhibitory effects on Hg0 oxidation at high temperatures when H2O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg2+ back into its elemental form. Data revealed that SO2 and NO were capable of promoting homogeneous reduction of Hg2+ to Hg0 with H2O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H2O was removed from the gas blend.     

Growth kinetics and competition between Methanosarcina and Methanosaeta in mesophilic anaerobic digestion.

Methanosarcina species with a high maximum specific growth rate (mumax) and high half-saturation coefficient (KS) and Methanosaeta species with a low mumax and low KS are the only known aceticlastic methanogens. Because of Methanosaeta's low KS, the low acetate concentrations in conventional, mesophilic anaerobic digestion yield Methanosaeta dominance. However, Methanosarcina absorbs increases in acetate more efficiently and thus promotes more stable digestion. This paper tests the hypothesis that decreasing digester feeding frequencies can increase Methanosarcina predominance. Two acetate-fed reactors were established at a 17-day solids retention time. One reactor was fed hourly, and one was fed once daily. Microscopic and molecular methods were used to verify that the hourly fed reactor enriched for Methanosaeta, while the daily fed reactor enriched for Methanosarcina. Growth and substrate-use kinetics were measured for each reactor. A digester overload condition was simulated, and the Methanosarcina-enriched reactor was found to perform better than the Methanosaeta-enriched reactor. These findings indicate that Methanosarcina dominance can be achieved with infrequent feedings, leading to more stable digestion.