Development of a continuously stirred flow cell for investigating sorption mass transfer

This paper introduces a new reversible-flow design for a continuously stirred reactor used to study sorption mass transfer in soil and solvent systems. The stirred reactor has potential advantages over conventional packed column or batch reactors because it isolates intraparticle sorption rate limitations from advective-dispersive transport, yet allows changes to flux through the reactor for analysis of sorption kinetics under dynamic conditions. Previously, stirred reactors have often failed due to clogging of sediment on the effluent frit. The reverse-flow backwashing design allows longer life and higher confidence in maintaining mixed conditions than previous designs. Mass transfer 'rate coefficients estimated from stirred and column experiments are compared; both techniques produced results consistent with a published correlation. The data also show that fitted sorption mass transfer coefficients can be strongly dependent on the choice of equilibrium partition coefficient (i.e. batch or first-moment derived values), and that the conventional two-site sorption kinetics model fails to accurately predict sorption mass transfer in the presence of changing solvent velocity through the reactor.     

Photochemical reduction of hexavalent chromium in glycerol-containing solutions

Hexavalent chromium [Cr(VI)] in the form of potassium dichromate was photochemically reduced to trivalent chromium [Cr(III)] in aqueous solutions containing glycerol. This reaction occurred rapidly during irradiation with either unfiltered sunlight or a UVA-emitting light source. Photochemical reduction of Cr(VI) was pH-dependent and did not occur in dilute solutions of sodium hydroxide. In acidified solutions, the reduction occurred at elevated rates and at lower concentrations of glycerol. This reaction was found to be dependent on the unsubstituted alcohol groups of glycerol since alpha-phosphoglycerol and beta-phosphoglycerol did not support the photochemical reduction of Cr(VI). These findings suggest that glycerol or related polyols can be used for the remediation of hexavalent (toxic) chromium at contaminated environmental sites.     

Methylmercury, fish consumption, and the precautionary principle

This paper considers several broad issues in the context of probabilistic assessment of the benefits of curtailing mercury (Hg) emissions from U.S. coal-fired power plants, based on information developed from recent literature and epidemiology studies of health effects of methylmercury. Exposure of the U.S. population is considered on the national scale, in large part because of recent questions arising from survey and experimental data about the relative importance of local deposition of airborne Hg. Although epidemiological studies have provided useful information, safe levels of Hg exposure remain uncertain, in part because of other dietary considerations in the populations that were studied. For example, much of the seafood consumed in one of the major studies was also contaminated with polychlorinated biphenyls, as are fish taken from some U.S. fresh waters. The primary epidemiological approach involves cross-study comparisons in relation to mean exposures, rather than detailed critiques of individual effects reported in each study. U.S. exposures are seen to be well below the levels at which adverse health effects are reported. This analysis supports the conclusion that unilateral reduction of Hg emissions from U.S. coal-fired power plants alone is unlikely to realize significant public health benefits.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Manganese toxicity thresholds for restoration grass species

Manganese toxicity thresholds for restoration plants have not been established. As a result, ecological risk assessments rely on toxicity thresholds for agronomic species, which may differ from those of restoration species. Our objective was to provide Mn toxicity thresholds for grasses commonly used in restoration. We used a greenhouse screening study where seedlings of redtop, slender wheatgrass, tufted hairgrass, big bluegrass, basin wildrye, and common wheat were grown in sand culture and exposed to increasing concentrations of Mn. The LC50, EC50-plant, EC50-shoot, EC50-root, PT50-shoot, and the PT50-root were then determined. Phytotoxicity thresholds and effective concentrations for the restoration species were generally higher than values reported for agronomic species. Our estimates of PT50-shoot for the five restoration grasses range from 41,528 to 120,082 mg Mn kg(-1). Measures of EC50-plant for these restoration grasses ranged from 877 to >6,000 mg Mn l(-1). These thresholds might be more useful for risk assessors than those based on crop plants that are widely used.     

Possible impacts of changes in UV-B radiation on North American trees and forests

Approximately 35 species representing 14 tree genera have been evaluated for responses to UV-B radiation in North America. The best representation has been in the conifers where some 20 species representing three genera have been studied. Overall, about 1/3 of these have demonstrated some deleterious response to UV-B. However, most negative impacts have been observed under controlled environment conditions where sensitivity may be enhanced. Therefore, it seems unlikely that expected levels of ozone depletion will result in direct losses in productivity. However, the role that ambient or enhanced levels of UV-B may play in forest ecosystem processes is more difficult to access. One possible indirect response of forests to changes in UV-B radiation levels could be via alterations in plant secondary metabolites. Increases in phenolics and flavonoids that enhance epidermal UV-screening effectiveness may also influence leaf development, water relations or ecosystem processes such as plant-herbivore interactions or decomposition.     

Metal partitioning in products of incineration of municipal solid waste

Metals contained in the waste transfer to the waste incineration products, including flue gas, fly ash, and bottom ash, as different oxide, nitride, carbides, and other phases. Most of the metal-based phases formed in incineration are toxic and their emissions need to be strictly controlled. Therefore, behavior of metal species during incineration must be well understood. Such understanding is possible based on the experimental identification of the metal phases formed in the waste combustion and determination of their concentration in various incineration products. To avoid well-known experimental difficulties of the industrial waste incinerators associated with the poor fuel/conditions reproducibility and limited instrumentation, a 140,000 Btu/h pilot-scale, laboratory burner was constructed, characterized and operated at NJIT. A synthetic fuel representative of the municipal solid waste in the US was formulated and produced in 600-Lb batches. The solid fuel contained Fe and SiO2 as main constituents, and was doped with trace amounts of Al, Ni, Cr, Hg and PbO. Several experiments have been conducted on combustion of the synthetic fuel in the pilot-scale incinerator with varying fuel-air equivalence ratio. Both gaseous and condensed combustion products were sampled and analyzed. Atomic absorption spectroscopy and X-ray diffraction were used to analyze total metal contents and metal containing phases in the incineration products. Thermodynamic equilibrium computations were performed to obtain the adiabatic flame temperature and identify the phases of the metal-containing products formed at the equilibrium conditions. The results of the equilibrium computations performed at the varied fuel/air ratios were compared with the observed experimental results.     

Lead removal from synthetic leachate matrices by a novel ion-exchange material

This paper discusses the application of a novel polyacrylate-based ion-exchange material for the removal of Pb ions from water. Preliminary testing includes the establishment of the operating pH range, capacity information, and the effect of Ca2+ and anions in the matrix. Batch testing with powder indicates slightly different optimal operational conditions from those used for column testing. The ion-exchanger is excellent for removing Pb from aqueous solutions.     

PAH deposition to snow surface

The urban snowpack effectively acts as a collection device for atmospheric-deposited PAHs. When these PAHs are flushed out in a short time interval along with springtime snowmelt, these cause shockloading to receiving waters. In order to assess the PAH deposition and accumulation in urban snowpacks, a deposition survey of PAH for the winter months of 1991-92 from the city of Sault Ste. Marie, Ontario, Canada was undertaken. The results of the survey are interpreted in view of prevailing meteorology and various emission sources in the study area. The relative PAH deposition levels (to BaP) are compared with relative source emission fingerprints to examine consistency in sampling and analysis. While analyzing the PAH samples using the ASTM (1987) method, the problem of concentration levels being below the detection level was encountered. The ASTM method for PAH analysis was modified to enhance the detection limit of the PAHs by concentrating the PAH extract to very low volumes, on the order of 200-300 microL.