Effect of sorption and desorption-resistance on biodegradation of chlorobenzene in two wetland soils.

Bioavailability of chlorobenzenes (CBs) in soils to microbial populations has implications for remediation of waste sites with long histories of contamination. Bioavailability of CB was assessed using mineralization assays for two types of wetland soils with contrasting properties. The rate and extent of CB mineralization were greater than predicted by mathematical models which assume instantaneous desorption followed by biodegradation. The freshly added CB was degraded with initial mineralization rates (IMRs) of 0.14microgL(-1)h(-1) and 1.92microgL(-1)h(-1) for marsh soil and wetland soil respectively. These values indicate that CB-degrading bacteria had an access to the sorbed CB. Mineralization assays were also performed for wetland soils after the CB was aged for 1, 7 and 31 days. The results revealed that even a desorption-resistant part of the sorbed CB was degraded although the degradation occurred at lower rates and to a lesser extent.

Chemical and microbiological parameters in New Orleans floodwater following Hurricane Katrina.

Hurricane Katrina, rated as a Category 4 hurricane on the Saffir-Simpson scale, made landfall on the U.S. Gulf Coast near New Orleans, Louisiana on Monday, August 29, 2005. The storm brought heavy winds and rain to the city, and several levees intended to protect New Orleans from the water of Lake Pontchartrain were breached. Consequently, up to 80% of the city was flooded with water reaching depths in excess of three meters in some locations. Research described in this paper was conducted to provide an initial assessment of contaminants present in floodwaters shortly after the storm and to characterize water pumped out of the city into Lake Pontchartrain once dewatering operations began several days after the storm. Data are presented which demonstrate that during the weeks following the storm, floodwater was brackish and well-buffered with very low concentrations of volatile and semivolatile organic pollutants. Dissolved oxygen was depleted in surface floodwater, averaging 1.6 mg/L in the Lakeview district and 4.8 mg/L in the Mid-City district. Dissolved oxygen was absent (< 0.02 mg/L) at the bottom of the floodwater column in the Mid-City district 9 days afterthe storm. Chemical oxygen demand (Mid-City average = 79.9 mg/L) and fecal coliform bacteria (Mid-City average = 1.4 x 10(5) MPN/100 mL) were elevated in surface floodwater but typical of stormwater runoff in the region. Lead, arsenic, and in some cases, chromium, exceeded drinking water standards but with the exception of some elevated Pb concentrations generally were typical of stormwater. Data suggest that what distinguishes Hurricane Katrina floodwater is the large volume and the human exposure to these pollutants that accompanied the flood, rather than very elevated concentrations of toxic pollutants.

Oxygen dynamics in petroleum hydrocarbon contaminated salt marsh soils: III. A rate model.

A model describing oxygen dynamics due to crude oil biodegradation under flooded conditions in saltwater wetlands was developed. The model is composed of three non-linear ordinary differential equations (ODEs) that simulate oxygen uptake, cell growth, and oil degradation simultaneously. The model equations were solved by using a stiff version of ODE solver, ODEPACK, which employs a multistep method and allows the change of step sizes and order of methods (ie., Gear's method). The results of model simulation were compared with experimental data obtained from a fully aerated microcosm study. The results of model simulation indicate that dissolved oxygen concentration in the overlying water rapidly depleted below 3 mg l(-1) unless the reaeration coefficient was higher than 2.0 day(-1). Active aerobic biodegradation of crude oil did not occur under flooded conditions because (i) dissolved oxygen is rapidly depleted, (ii) reaeration is not sufficient enough to replenish dissolved oxygen and (iii) the oil dissolution rate constant decreases over time. The model may lead to better understanding of oxygen demand for a long bioremediation period. The results of this study may be applicable for the establishment of an engineered bioremediation strategy.

Rate-limited desorption of volatile organic compounds from soils and implications for the remediation of a Louisiana Superfund site.

The rates of desorption of trichloroethylene (TCE) and 1,3-dichlorobenzene (DCB) from a silty soil at a Superfund site and a silty-clayey soil from an uncontaminated bottomland hardwood swamp in Baton Rouge, Louisiana were studied in laboratory batch systems. The effect of the age of soil contamination was studied using a laboratory-spiked soil incubated for 3 days, 3 months and 5 months. An empirical non-linear model was used to describe the bi-phasic nature of desorption with one fraction (labile) being released in relatively short periods of time (typically 24-100 hr) and a second fraction (non-labile or irreversible) being resistant to desorption. The non-linear model parameters, viz., the fraction of the chemical released rapidly (F), and the first order desorption rate coefficients, k1 and k2 respectively for the labile and slowly released fractions were determined by fitting the experimental data to the model. The data fit the model well as indicated by the high r2 values. The estimate of k1 was good. However, the values of k2 are known with less precision due to the limited duration of the experiment and number of samples taken at long times. In addition, desorption kinetics of 3 and 5-month old contaminated soils showed that progressively less amount of contaminant was available for facile desorption (lower F) compared to freshly contaminated soil. The labile fraction had desorption rate constants of the order of 10(-1) h(-1), whereas the slowly released fraction had rate constants of the order of 10(-4) h(-1) in accord with literature reported values for a variety of other compounds and soils. Possible mechanisms describing these rates and implications for the site clean up are discussed.

Oxygen dynamics in crude oil contaminated salt marshes: I. Aerobic respiration model.

A simple model was developed to predict oxygen demand exerted by aerobic biodegradation of spilled crude oil and fertilizer added to stimulate biodegradation in salt marsh sediment. The role of aerobic respiration (AR) was determined using first-order G kinetics. The G kinetic rate constants were calculated from laboratory data sets through linear regression. The effect of oil and fertilizer on AR was quantified by comparing three treatments: (i) control (no oil and fertilizer amended), (ii) fertilized, and (iii) oiled and fertilized sediments. The effects of dissolved oxygen concentration in the overlying water and surface mass transfer coefficient were investigated. Aerobic respiration was strongly dependent on the overlying dissolved oxygen concentration when crude oil and fertilizer were added. Oiled/fertilized cores did not show higher SOD and AR than control cores when overlying DO concentration dropped below 5 mg l(-1). Results indicate that higher aerobic respiration in oiled/fertilized is exerted by aerobic biodegradation of crude oil and that major biodegradation of crude oil occurs only when DO level is high (> 5 mg l(-1)).

Oxygen dynamics in crude oil contaminated salt marshes: II. Carbonaceous sediment oxygen demand model.

The role of carbonaceous sediment oxygen demand (CSOD) due to oxidation of sulfides reduced in oxygen dynamics in crude oil contaminated salt marshes was investigated through a mathematical model. An existing CSOD model was calibrated from laboratory data sets through nonlinear regression. The effect of oil and fertilizer on CSOD was quantified by comparing three treatments (i) control (no oil and fertilizer amended) (ii) fertilized, and (iii) oiled and fertilized sediments. CSOD was directly proportional to sulfate reduction. Higher CSODs under oiled/fertilized and fertilized conditions were primarily due to increased sulfate reduction rates under these conditions. Reaction velocity for oxidation of dissolved sulfide in the aerobic layer, kappaH2S,d1, was significantly greater than that of particulate sulfide oxidation, kappaH2S,p1. This indicates that dissolved sulfides are dominant over particulate sulfides and directly related to CSOD in salt marshes. The CSOD was linearly dependent on the overlying dissolved oxygen concentration when crude oil and fertilizer were added.

Leaf gas exchange and growth of flood-tolerant and flood-sensitive tree species under low soil redox conditions.

Seedlings of Taxodium distichum L., Quercus lyrata Walt. and Q. falcata var. pagodaefolia Ell. were grown for 22 days in a rhizotron system providing two soil redox potential regimes, +170 mV (low Eh) and +560 mV (high Eh). Leaf chlorophyll concentration and gas exchange, root alcohol dehydrogenase (ADH) activity, root and leaf ethylene production, and growth and biomass partitioning were measured. In response to the low Eh soil treatment, stomatal conductance was reduced in Q. falcata and Q. lyrata but not in T. distichum, whereas net photosynthesis was reduced significantly in all species; however, net photosynthesis in T. distichum began to recover within 2 weeks of treatment initiation. Within each treatment, mean stomatal conductance and net photosynthesis were significantly greater in T. distichum than in the oak species. Leaf chlorophyll concentration was not affected by the soil treatments. All species showed significant reductions in root and leaf dry weights in response to the low Eh soil condition. The low Eh soil treatment resulted in increased root ADH activity and ethylene production in T. distichum, but had no effect on root ADH activity and ethylene production in the oak species.

Effect of redox potential on fixation of 137Cs in lake sediment.

Fixation of 137Cs was determined in lake sediment suspensions under controlled redox potentials in the laboratory. The activity of previously added 137Cs on various clay sites was determined by time-series selective extractions. Monovalent cations, particularly NH+4, were much more effective at displacing 137Cs than divalent cations or Na+. Ammonium ion (NH+4) and Na+ were used to extract 137Cs from selective and non-selective 137Cs-binding sites, respectively. The activity of water-soluble 137Cs and Na-extractable 137Cs was significantly higher under anaerobic redox conditions (-200 mV), when soluble NH+4 concentrations in the anaerobic suspensions were 1000 microM or higher. Activities of 137Cs were highest (initially 40-50% of the 137Cs added) on the NH+4-extractable site. Over the long term, activities of NH+4-extractable 137Cs decreased linearly to below 10% as 137Cs was fixed on inter-lattice sites. Water-soluble 137Cs was significantly correlated with Na-extractable 137Cs in short-term experiments, suggesting the existence of an equilibrium between the different clay sites. High concentrations of NH+4 under anaerobic redox conditions could shift this equilibrium, resulting in increases in water-soluble 137Cs and increases in the activities of 137Cs bound on non-selective clay sites. Additional studies are necessary to evaluate the interaction of 137Cs with sulfides, iron oxides, and other reactive chemical species which may attenuate 137Cs in sediment.