Simulating bioremediation of uranium-contaminated aquifers; uncertainty assessment of model parameters

Bioremediation of trace metals and radionuclides in groundwater may require the manipulation of redox conditions via the injection of a carbon source. For example, after nitrate has been reduced, soluble U(VI) can be reduced simultaneously with other electron acceptors such as Fe(III) or sulfate to U(IV), which may precipitate as a solid (uraninite).To simulate the numerous biogeochemical processes that will occur during the bioremediation of trace-metal-contaminated aquifers, a time-dependent one-dimensional reactive transport model has been developed. The model consists of a set of coupled mass balance equations, accounting for advection, hydrodynamic dispersion, and a kinetic formulation of the biological or chemical transformations affecting an organic substrate, electron acceptors, corresponding reduced species, and trace metal contaminants of interest, uranium in this study. This set of equations is solved numerically, using a finite difference approximation. The redox conditions of the domain are characterized by estimating the pE, based on the concentration of the dominant terminal electron acceptor and its corresponding reduced species. This pE and the concentrations of relevant species are then used by a modified version of MINTEQA2, which calculates the speciation/sorption and precipitation/dissolution of the species of interest under equilibrium conditions. Kinetics of precipitation/dissolution processes are described as being proportional to the difference between the actual and calculated equilibrium concentration. A global uncertainty assessment, determined by Random Sampling High Dimensional Model Representation (RS-HDMR), was performed to attain a phenomenological understanding of the origins of output variability and to suggest input parameter refinements as well as to provide guidance for field experiments to improve the quality of the model predictions. By decomposing the model output variance into its different input contributions, RS-HDMR can identify the model inputs with the most influence on various model outputs, as well as their behavior pattern on the model output. Simulations are performed to illustrate the effect of biostimulation on the fate of uranium in a saturated aquifer, and to identify the key processes that need to be characterized with the highest accuracy prior to designing a uranium bioremediation scheme.     

Solute transport modeling under cultivated sandy soils and transient water regime

Drainable lysimeters offer the possibility to integrate heterogeneous solute leaching conditions caused by row crops and transient water regime, and to conveniently measure water and solute fluxes at the drainage outlet. To compare solute leaching behavior in and around drainable lysimeters operating under a transient water regime in potato (Solanum tuberosum L.) fields, parameters of the convective lognormal transfer (CLT) function model were fitted using bromide (Br-) flux concentrations (Cf) measured in lysimeters and from Br- resident concentrations (Cr) measured in adjacent soil cores. Expected mean values Ez(I) obtained from Cr and Cf CLT parameters were equivalent and well correlated (R2 = 0.78). However, estimated median values mu of the CLT function were smaller when derived from Cr (1.05 to 1.28) compared with Cf (1.23 to 2.14). Most mu values were also smaller than previously reported values for a 30-cm reference depth, indicating that 50% of solute mass would leach more readily in these coarse sandy soils. Higher variance and dispersion of Cr compared with those of Cf could be related to a smaller sampling support (sample size/sampling area) in the case of Cr measured by soil coring, or to disruption of solute transport mechanisms in the repacked lysimeter. Retained Br- in the top soil layer after 12 to 17 cm of cumulative drainage was indicated by measured Cr. Neither CLT function simulated well residual topsoil Cr values, indicating that Br- plant cycling or preferential flow probably interfered even though tuber Br- uptake was relatively small.     

Obituary

Water, Air, &; Soil Pollution: Focus -     

Pseudomonas lemoignei has five poly(hydroxyalkanoic acid) (PHA) depolymerase genes: A comparative study of bacterial and eukaryotic PHA depolymerases

Four polyhydroxyalkanoate (PHA) depolymerases were purified from the culture fluid ofPseudomonas lemoignei: poly(3-hydroxybutyrate) (PHB), depolymerase A (M _r , 55,000), and PHB depolymerase B (M _r , 67,000) were specific for PHB and copolymers of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) as substrates. The third depolymerase additionally hydrolyzed poly(3-hydroxyvalerate) (PHV) at high rates (PHV depolymerase;M _r , 54,000). The N-terminal amino acid sequences of the three purified proteins, of a fourth partially purified depolymerase (PHB depolymerase C), and of the PHB depolymerases ofComamonas sp. were determined. Four PHA depolymerase genes ofP. lemoignei (phaZ1,phaZ2,phaZ3, andphaZ4) have been cloned inEscherichia coli, and the nucleotide sequence ofphaZ1 has been determined recently (D. Jendrossek, B. Müller, and H. G. Schlegel,Eur. J. Biochem. 218, 701–710, 1993). In this study the nucleotide sequences ofphaZ2 andphaZ3 were determined.PhaZ1,phaZ2, andphaZ4 were identified to encode PHB depolymerase C, PHB depolymerase B, and PHV depolymerase, respectively.PhaZ3 coded for a novel PHB depolymerase ofP. lemoignei, named PHB depolymerase D. None of the four genes harbored the PHB depolymerase A gene, which is predicted to be encoded by a fifth depolymerase gene ofP. lemoignei (phaZ5) and which has not been cloned yet. The deduced amino acid sequences ofphaZ1–phaZ3 revealed high homologies to each other (68–72%) and medium homologies to the PHB depolymerase gene ofAlcaligenes faecalis T₁ (25–34%). Typical leader peptide amino acid sequences, lipase consensus sequences (Gly-Xaa-Ser-Xaa-Gly), and unusually high proportions of threonine near the C terminus were found in PhaZ1, PhaZ2, and PhaZ3. Considering the biochemical data of the purified proteins and the amino acid sequences, PHA depolymerases ofP. lemoignei are most probably serine hydrolases containing a catalytical triad of Asp, His, and Ser similar to that of lipases. A comparison of biochemical and genetic data of various eubacterial and one eukaryotic PHA depolymerases is provided also.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Development and application of an ecosystem management approach for protected natural areas

Preservation of small natural areas is not in itself a sufficient measure to maintain the integrity of the ecosystems for which they were initially set aside. Intense pressure from recreational use is just one of the many human-caused stresses that may degrade natural areas. Therefore, land-use planning and management from an ecological perspective is necessary to assess, ensure, and in some cases increase, the ecological integrity of protected natural areas. An ecosystem management approach for small protected natural areas with high recreational use is presented, based on three interrelated components: an ecological evaluation procedure of ecosystems, the implementation of management interventions on ecosystems, and the development of a monitoring scheme of ecosystem components. The ecological evaluation procedure combines two concepts: the biotic value of vegetation and wildlife and the abiotic fragility of the soils. This combined evaluation process results in the creation of a sensitivity map that can be used as a management tool for planners and managers. Management interventions, the second component of the management approach, are derived from concepts of ecological succession. Intentional human interventions are used to maintain the ecological integrity of ecosystems or in some cases to restore degraded sites. For the third component, only the basic principles of the monitoring program will be discussed. A pilot project in one of the Montreal urban community protected areas is presented to illustrate aspects of the proposed ecosystem management approach.     

Catalytic upgrading of higher 1-alkenes from polyethylene thermal cracking by modified Wacker oxidation

The economic success of feedstock recycling procedures for plastic wastes is increasingly demanding the conversion of the starting residue into more valuable chemicals. Thermal cracking of polyethylenes leads to the preparation of equimolar mixtures of n-paraffins and 1-alkenes within the C₂–C₁₀₀ range. These 1-olefins can be catalytically upgraded by selective oxidation processes to more valuable products (e.g., ketones and fatty acids) with different uses such as polar waxes, cetane improvers, varnishes, and printer inks. The results obtained on oxidation in a modified Wacker system of a model 1-olefin (1-dodecene) as well as of a distillate cut (C₁₀–C₂₅) of the product from the thermal cracking of urban polyethylene waste are described.     

Phytoaccumulation of heavy metals by aquatic plants

Three aquatic plants were examined for their ability to remove heavy metals from contaminated water: parrot feather (Myriophylhum aquaticum), creeping primrose (Ludwigina palustris), and water mint (Mentha aquatic). The plants were obtained from a Solar Aquatic System treating municipal wastewater. All the three plants were able to remove Fe, Zn, Cu, and Hg from the contaminated water. The average removal efficiency for the three plant species was 99.8%, 76.7%, 41.62%, and 33.9% of Hg, Fe, Cu, and Zn, respectively. The removal rates of zinc and copper were constant (0.48 mg/l/day for Zn and 0.11 mg/l/day for Cu), whereas those of iron and mercury were dependent on the concentration of these elements in the contaminated water and ranged from 7.00 to 0.41 mg/l/day for Fe and 0.0787 to 0.0002 mg/l/day for Hg. Parrot feather showed greater tolerance to toxicity followed by water mint and creeping primrose. The growth of creeping primrose was significantly affected by heavy metal toxicity. The selectivity of heavy metals for the three plant species was the same (Hg>Fe>Cu>Zn). The mass balance preformed on the system showed that about 60.45-82.61% of the zinc and 38.96-60.75% of the copper were removed by precipitation as zinc phosphate and copper phosphate, respectively.     

Greenhouse gases fluxes and soil thermal properties in a pasture in central Missouri

Fluctuations of greenhouse gases emissions and soil properties occur at short spatial and temporal scales, however, results are often reported for larger scales studies. We monitored CO2, CH4, and N2O fluxes and soil temperature (T), thermal conductivity (K), resistivity (R) and thermal di usivity (D) from 2004 to 2006 in a pasture. Soil air samples for determination of CO2, CH4 and N2O concentrations were collected from static and vented chambers and analyzed within two hours of collection with a gas chromatograph. T, K, R and D were measured in-situ using a KD2 probe. Soil samples were also taken for measurements of soil chemical and physical properties. The pasture acted as a sink in 2004, a source in 2005 and again a sink of CH4 in 2006. CO2 and CH4 were highest, but N2O as well as T, K and D were lowest in 2004. Only K was correlated with CO2 in 2004 while T correlated with both N2O (r = 0.76, p = 0.0001) and CO2 (r = 0.88, p = 0.0001) in 2005. In 2006, all gases fluxes were significantly correlated with T, K and R when the data for the entire year were considered. However, an in-depth examination of the data revealed the existence of month-to-month shifts, lack of correlation and di ering spatial structures. These results stress the need for further studies on the relationship between soil properties and gases fluxes. K and R o er a promise as potential controlling factors for greenhouse gases fluxes in this pasture.     

Evaluation of the effectiveness of horizontal subsurface flow constructed wetlands for different media

Two media bed (gravel and Filtralite NR) were tested in a mesocosm to evaluate the removal of organic matter (as chemical oxygen demand (COD)),ammonia (NH4-N),nitrite,nitrate and solid matter (as total suspended solids (TSS)) for a synthetic wastewater (acetate-based) and a domestic wastewater.The use of Filtralite allowed average removal rates (6–16.8 g COD/(m2·day),0.8–1.1 g NH4-N/(m2·day) and 3.1 g TSS/(m2·day)) and removal effciencies (65%–93%,57%–85% and 78% for COD,NH4-N and TSS,respectively),higher than that observed in the experiments with gravel.The applied loads of COD,ammonia,nitrate and TSS seem to influence the respective removal rates but only for the treatment of domestic wastewater with higher correlation coefficients for Filtralite.Regardless the type of media bed and the type of wastewater,nitrate was completely removed for nitrogen loading rates up to 1.3 g NO3-N/(m2·day).There was no evidence of the influence of nitrate loads on the removal of organic matter.