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A whole-core injection method was used to determine depth-related rates of microbial mineralization of (14)C-phenanthrene added to both contaminated and clean marine sediments of Puget Sound, WA. For 26-day incubations under micro-aerobic conditions, conversions of (14)C-phenanthrene to (14)CO(2) in heavily PAH-contaminated sediments from two sites in Eagle Harbor were much higher (up to 30%) than those in clean sediments from nearby Blakely Harbor (3%). The averaged (14)C-phenanthrene degradation rates in the surface sediment horizons (0-3 cm) were more rapid (2-3 times) than in the deeper sediment horizons examined (6 cm), especially in the most PAH polluted EH9 site. Differences in mineralization were associated with properties of the sediments as a function of sediment depth, including grain-size distribution, PAH concentration, total organic matter and total bacterial abundance. When strictly anaerobic incubations (in N(2)/H(2)/CO(2) atmosphere) were used, the phenanthrene biodegradation rates at all sediment depths were two times slower than under micro-aerobic conditions, with methanogenesis observed after 24 days. The main rate-limiting factor for phenanthrene degradation under anaerobic conditions appeared to be the availability of suitable electron acceptors. Addition of calcium sulfate enhanced the first order rate coefficient (k(1) increased from 0.003 to 0.006 day(-1)), whereas addition of soluble nitrate, even at very low concentration (0.5 mM), inhibited mineralization. Long-term storage of heavily polluted Eagle Harbor sediment as intact cores under micro-aerobic conditions also appeared to enhance anaerobic biodegradation rates (k(1) up to 0.11 day(-1)).

To advance the accuracy of bioremediation measurements, it is useful before specific experiments to attribute or estimate the influence of both experimental as well as field conditions on the expected magnitudes of microbial degradation rate coefficients. This paper analyzes the numerical contribution, or influence, of categories of conditions, such as bacterial adaptive state, electron acceptor type, mixing, generalized sorption conditions, and biodegradation temperature, on published phenanthrene biodegradation rates as an example of our regression approach. A fundamental microbial degradation rate equation is transformed to an additive model, then using multiple linear regression on published data, coefficients (of categorical variables) and a linear model are presented that estimate first-order biodegradation rate coefficients to within a factor of 3. Numerical estimates of how much bacterial adaptive state and presence of a sorption phase, the two most statistically significant factors, alter the phenanthrene biodegradation rate are presented. The influence of some measurement or field conditions, for example, the influence of oxygen reduction versus optimal nitrate reduction, cannot be distinguished statistically given the available data and range. The regression model is tested using conditions from newly published papers to estimate a priori the expected rate, which compares very favorably to measurements reported in the papers. Due to limited published data and range for extreme cases, the current coefficients do not apply to degradation of very aged phenanthrene nor very low concentrations of electron acceptors. As estimating tools, however, the coefficients themselves and the regression approach have very beneficial roles in design of experiments for both laboratory and field settings. Our method can be applied to other PAHs as sufficient data become available.

Experimental measurements demonstrated that rates of in situ microbial anaerobic biodegradation of phenanthrene in undisturbed marine sediments were enhanced when controlled-release electron acceptors (i.e., nitrate and sulfate (for comparison)) were employed. The experimental method used whole and interval cores injected with radiolabeled 14C-phenanthrene, which were incubated, sacrificed, and processed for 14CO2 recovery to determine degradation rates. Nitrocellulose and CaSO4 were formulated to release the electron acceptors into the sediments at rates consistent with bacterial utilization (i.e., that avoided inhibition observed previously at high soluble nitrate (although not sulfate) concentrations). The controlled-release of both compounds, measured in collateral experiments, enhanced the natural anaerobic phenanthrene biodegradation rates by factors up to 2-3. Biodegradation via sulfate reduction was most rapid in the early stages (24 days) of experiments, consistent with reports that many marine bacteria in submerged sediments are sulfate reducers. In comparison, in longer experiments (after 42 days), the anaerobic biodegradation rates were observed at least as high with the addition of nitrocellulose (over 40% of added phenanthrene recovered as 14CO2). Both nitrate and sulfate reduction was observed during anaerobic incubation, although the presence of nitrate seemed to reduce the sulfate reduction. The studied forms of the controlled-release nitrate and sulfate may provide capping amendments to decontaminate marine harbor sediments.

Extracellular enzymes are important agents for microbial foraging and material cycling in diverse natural and man-made systems. Their abundance and effects are analyzed empirically on scales much larger than the forager. Here, we use a modelling approach to analyze the potential costs and benefits, to an individual immobile microbe, of freely releasing extracellular enzymes into a fluid-bathed, stable matrix of both inert and food-containing particles. The target environments are marine aggregates and sediments, but the results extend to biofilms, bioreactors, soils, stored foods, teeth, gut contents, and even soft tissues attacked by disease organisms. Model predictions, consistent with macroscopic observations of enzyme activity in laboratory and environmental samples, include: support of significant bacterial growth by cell-free enzymes; preponderance of particle-attached, as opposed to dissolved, cell-free enzymes; solubilization of particulate substrates in excess of resident microbe growth requirements; and constitutive, abundant enzyme release in some environments. Feeding with cell-free enzymes appears to be limited to substrates within a well-defined distance of the enzyme source. Fluxes of dissolved organic material out of pelagic oceanic aggregates and marine sediments, and difficulty detecting dissolved enzymes in such environments, may reflect characteristics of cell-free enzyme foraging and properties of the enzymes. Our calculations further suggest that cell-free enzymes may often be used by microorganisms as the fastest means to search for food.

The authors present experimentally measured devolatilization product yields from single particles of refuse-derived fuel (RDF), a more uniform, transportable municipal solid waste. Disposal costs and environmental concerns have stimulated interest in thermochemical conversion of this material to chemicals and fuels. The composition, reaction conditions, and particle properties were systematically varied over the range found in practice to develop quantitative measures that rank the process controllables' influence on altering the product slate. Specialized regression methods and experimental designs enhanced the accuracy in view of the feed heterogeneity and offer a general method to extract real effects from experimental and sample noise''. The results have been verified successfully using actual commercial RDF and fabricated compositions that surpass those normally found in municipal waste to anticipate the influence of trends in recycling. The results show that the reaction conditions have a greater influence on altering fuel utilization and the relative yields of char, condensibles, and gases than does the composition over the range found in MSW and RDF.

Practices to minimize pollutants from municipal solid waste combustion devices include preparation steps to provide relatively uniform feed particles. This is the rationale behind commercially available densified refuse-derived fuel (d-RDF). However the solid phase devolatilization rate, the composition and rate of production of reaction products and pollutants, and the influence of waste feed properties on these processes have not been quantified. Devolatilization experiments were performed on single, well-characterized d-RDF particles under carefully controlled conditions of practical importance. Intrapar-ticle temperature histories, gas evolution rates and compositions were measured. The results presented here quantify the simultaneous effects of both initial moisture and particle heating rate on the intraparticle temperature field which controls the extent of local reaction. It appears moisture does not strongly alter the overall production of both gases and condensibles (tars) from the devol...

Rates of 14C-phenanthrene mineralization in contaminated, undisturbed marine sediments were measured using the whole core injection method to assess microbial natural attenuation activity as a function of sediment depth. Submerged sediments were sampled from Eagle Harbor, a marine superfund site in Puget Sound. Experiments show significant biodegradation activities (0.0012-0.0036 day(-1)) in the sediment horizons from 0 to 10 cm. The purpose and scope of this paper is to evaluate the range of experimental conditions giving valid results; a mathematical simulation described competing contaminant 14C-phenanthrene diffusion and simultaneous biodegradation (Monod kinetics), both retarded by sorption. The effect of aging was examined with two sorption models in presumed pseudo-homogenous sediments having effective properties. The simulation predictions provide quantitative guidelines for the successful use of the whole core injection method. (1) The effective Monod constant KS' in sediment is increased by a large partition coefficient KP between sediment and water and makes the apparent 14C-phenanthrene biodegradation approach first-order kinetics. (2) When KS'>1 mg(-1) l(-1), the measured 14C-phenanthrene biodegradation extent is biased by inadequately distributed injected tracer only when less than 7% of the sediment horizon is initially probed and mixed with injected tracer. (3) A short incubation time (

A primary goal of this ongoing research is to quantitatively measure the effects of feedstock composition on the pyrolysis of biomass. Two classes of biomass are studied: municipal solid waste (refuse-derived fuel) which is over 80% lignocellulosics, and under-utilized herbaceous and woody species. The composition classes within municipal solid waste were easily identified, and experiments were performed to quantify the effects of paper, plastics, metal/and glass, and inorganics content on the pyrolysis product slate. The influence of reaction conditions (heating rate) and feed properties (moisture and particle size) were also studied in conjunction with the composition effects. The composition measures for biomass relied on characterization data from the US Department of Agriculture on over 1100 species.

Single, thermally thick particles of lodgepole pinewood were pyrolyzed under well-defined conditions of industrial importance. Particle thickness, heating level, moisture content, density, and grain axis relative to one-dimensional heating were varied using a Box-Behnken experimental design. Gross product fractions, as well as components therein, were measured and the batch yields were correlated with second-order polynomials. The empirical equations correlating the batch yields, together with their prediction uncertainties, are presented and are suitable for use in simulations of wood combustion and thermal conversion. Comparison of large particle pyrolysis product distributions to other studies of small-particle pyrolysis yields shows the trends with particle size to be consistent. Tar yield minima depend on both particle size and heating rate. Gas yield is dependent on both particle size and heating intensity. Because some process controllables were found to alter product yields from large particles in a multiplicative way, rather than an additive way, suggestions for future experiments are made.

Though it is generally acknowledged that biomass feed properties such as moisture content, density, thermal properties, and particle size alter its devolatilization products, the magnitudes of the effects are not well known. Such knowledge is needed for the successful development of biomass thermal conversion processes since feed properties such as particle size and moisture content should be chosen, or perhaps altered by pretreatment, to optimize the products formed during initial heating. To aid in determining optimum feed properties, expecially in combination with given process conditions, a detailed simulation of wood devolatilization has been developed, validated by comparison to experiments performed under a wide variety of conditions of industrial importance, and predictions are presented here. Also, the sensitivity of pyrolysis yields to such quantities as the uncertainty in kinetic parameters for the decomposition mechanism or thermal property variations are presented.