Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.     

Simplified contaminant source depletion models as analogs of multiphase simulators

Four simplified dense non-aqueous phase liquid (DNAPL) source depletion models recently introduced in the literature are evaluated for the prediction of long-term effects of source depletion under natural gradient flow. These models are simple in form (a power function equation is an example) but are shown here to serve as mathematical analogs to complex multiphase flow and transport simulators. The spill and subsequent dissolution of DNAPLs was simulated in domains having different hydrologic characteristics (variance of the log conductivity field=0.2, 1 and 3) using the multiphase flow and transport simulator UTCHEM. The dissolution profiles were fitted using four analytical models: the equilibrium streamtube model (ESM), the advection dispersion model (ADM), the power law model (PLM) and the Damkohler number model (DaM). All four models, though very different in their conceptualization, include two basic parameters that describe the mean DNAPL mass and the joint variability in the velocity and DNAPL distributions. The variability parameter was observed to be strongly correlated with the variance of the log conductivity field in the ESM and ADM but weakly correlated in the PLM and DaM. The DaM also includes a third parameter that describes the effect of rate-limited dissolution, but here this parameter was held constant as the numerical simulations were found to be insensitive to local-scale mass transfer. All four models were able to emulate the characteristics of the dissolution profiles generated from the complex numerical simulator, but the one-parameter PLM fits were the poorest, especially for the low heterogeneity case.     

Diffusion of PAH and PCB from contaminated sediments with and without mineral capping; measurement and modelling

A novel laboratory microcosm test was developed to measure the diffusion of native PAHs and PCBs from sediments in the presence and absence of a capping layer. Diffusive flux of 15 PAHs and 7 PCBs from uncapped sediment from Oslo harbour was 3.8+/-0.9 microg m(-2)d(-1) and 0.010+/-0.003 microg m(-2)d(-1), respectively. The flux from sediments capped with 1cm mineral cap (crushed limestone or crushed gneiss (0-2mm)), observed during the first 410 d, was 3.5-7.3% of the flux from uncapped sediments. By measuring freely dissolved pore water concentrations of 10 PAHs the flux in the microcosm was modelled with steady state and transient diffusion models. The measured flux from uncapped sediment was 27-290% of modelled steady state flux. Good agreement was also found between the measured flux of pyrene from capped sediment and the flux modelled with the transient model when fitting only with the distribution coefficients for pyrene between the cap material and water (Kd_pyr). Fitted Kd_pyr, (210 and 23 l kg(-1) for limestone and gneiss, respectively) was in the same order of magnitude as K(d) calculated from organic carbon content in the cap materials (68 and 14 l kg(-1) respectively). Calculation of the efficiency of a hypothetical cap with 10 cm diffusion path shows that the increased diffusion path length alone can yield a flux reduction >99% through a strong increase in the stagnant diffusive boundary layer from <1 to 100mm.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Coupled infrared extinction spectra and size distribution measurements for several non-clay components of mineral dust aerosol (quartz, calcite, and dolomite)

Simultaneous size distributions and Fourier transform infrared (FTIR) extinction spectra have been measured for several representative components of mineral dust aerosol (quartz, calcite, and dolomite) in the fine particle size mode (D=0.1–1 μm). Optical constants drawn from the published literature have been used in combination with the experimentally determined size distributions to simulate the extinction spectra. In general, Mie theory does not accurately reproduce the peak position or band shape for the prominent IR resonance features in the 800–1600 cm⁻¹ spectral range. The resonance peaks in the Mie simulation are consistently blue shifted relative to the experimental spectra by 20–50 cm⁻¹. Spectral simulations, derived from a simple Rayleigh-based analytic theory for a “continuous distribution of ellipsoids” particle shape model, better reproduce the experimental spectra, despite the fact that the Rayleigh approximation is not strictly satisfied in these experiments. These results differ from our previous studies of particle shape effects in silicate clay mineral dust aerosols where a disk-shaped model for the particles was found to be more appropriate.     

A directional passive air sampler for monitoring polycyclic aromatic hydrocarbons (PAHs) in air mass

A passive air sampler was developed for collecting polycyclic aromatic hydrocarbons (PAHs) in air mass from various directions. The airflow velocity within the sampler was assessed for its responses to ambient wind speed and direction. The sampler was examined for trapped particles, evaluated quantitatively for influence of airflow velocity and temperature on PAH uptake, examined for PAH uptake kinetics, calibrated against active sampling, and finally tested in the field. The airflow volume passing the sampler was linearly proportional to ambient wind speed and sensitive to wind direction. The uptake rate for an individual PAH was a function of airflow velocity, temperature and the octanol-air partitioning coefficient of the PAH. For all PAHs with more than two rings, the passive sampler operated in a linear uptake phase for three weeks. Different PAH concentrations were obtained in air masses from different directions in the field test.     

Degradation and plant uptake of nonylphenol (NP) and nonylphenol-12-ethoxylate (NP12EO) in four contrasting agricultural soils

Nonylphenol polyethoxylates (NPEOs) are surfactants found ubiquitously in the environment due to widespread industrial and domestic use. Biodegradation of NPEOs produces nonylphenol (NP), an endocrine disruptor. Sewage sludge application introduces NPEOs and NP into soils, potentially leading to accumulation in soils and crops. We examined degradation of NP and nonylphenol-12-ethoxylate (NP12EO) in four soils. NP12EO degraded rapidly (initial half time 0.3-5 days). Concentrations became undetectable within 70-90 days, with a small increase in NP concentrations after 30 days. NP initially degraded quickly (mean half time 11.5 days), but in three soils a recalcitrant fraction of 26-35% remained: the non-degrading fraction may consist of branched isomers, resistant to biodegradation. Uptake of NP by bean plants was also examined. Mean bioconcentration factors for shoots and seeds were 0.71 and 0.58, respectively. Removal of NP from the soil by plant uptake was negligible (0.01-0.02% of initial NP). Root concentrations were substantially higher than shoot and seed concentrations.     

Role of blue green algae biofertilizer in ameliorating the nitrogen demand and fly-ash stress to the growth and yield of rice (Oryza sativa L.) plants

Rice is a major food crop throughout the world; however, accumulation of toxic metals and metalloids in grains in contaminated environments is a matter of growing concern. Field experiments were conducted to analyze the growth performance, elemental composition (Fe, Si, Zn, Mn, Cu, Ni, Cd and As) and yield of the rice plants (Oryza sativa L. cv. Saryu-52) grown under different doses of fly-ash (FA; applied @ 10 and 100 tha(-1) denoted as FA(10) and FA(100), respectively) mixed with garden soil (GS) in combination with nitrogen fertilizer (NF; applied @ 90 and 120 kg ha(-1) denoted as NF(90) and NF(120), respectively) and blue green algae biofertilizer (BGA; applied @ 12.5 kg ha(-1) denoted as BGA(12.5)). Significant enhancement of growth was observed in the plants growing on amended soils as compared to GS and best response was obtained in amendment of FA(10)+NF(90)+BGA(12.5). Accumulation of Si, Fe, Zn and Mn was higher than Cu, Cd, Ni and As. Arsenic accumulation was detected only in FA(100) and its amendments. Inoculation of BGA(12.5) caused slight reduction in Cd, Ni and As content of plants as compared to NF(120) amendment. The high levels of stress inducible non-protein thiols (NP-SH) and cysteine in FA(100) were decreased by application of NF and BGA indicating stress amelioration. Study suggests integrated use of FA, BGA and NF for improved growth, yield and mineral composition of the rice plants besides reducing the high demand of nitrogen fertilizers.     

Evaluation of post-Katrina flooded soils for contaminants and toxicity to the soil invertebrates Eisenia fetida and Caenorhabditis elegans

This research evaluated soil samples from a New Orleans neighborhood in the Chalmette, Saint Bernard Parish, that had been inundated by flooding associated with Hurricane Katrina. The goal was to determine if ecological risks persisted from flood waters that had come in contact with hazardous surface chemicals before inundating this low-lying neighborhood for a prolonged period. Research objectives were to establish the presence or absence of volatile organic and heavy metal contaminants, and then asses the toxicity of this soil to Eisenia fetida in a soil exposure assay and Caenorhabditis elegans in a simulated porewater exposure assay. Soil analysis revealed detectable levels of metals and organics in the surface soil at each location. No contaminant was detected in concentrations above human health screening values. Chromium and mercury were detected at levels in excess of typical ecological risk values. Soil extracts revealed concentrations of nitrate, sulfate, and chloride above those from an unflooded background sample. Toxicity testing resulted in no acute effects to either test species, but did show bioaccumulation of arsenic, cadmium, and lead in E. fetida exposed to several samples. The combination of mercury and sulfate provide the potential for mercury methylation should flooding and prolonged inundation occur again.     

Enhancement of the CO(2) retention capacity of X zeolites by Na- and Cs-treatments

Adsorption of carbon dioxide on alkaline modified X zeolites was investigated by temperature programmed desorption (TPD) analysis of these materials previously saturated with CO(2) at 50, 100 and 200 degrees C. Parent X zeolite (in its sodium form) was treated with different sodium and cesium aqueous solutions, using both carbonates and hydroxides as precursors. The resulting materials were characterised by nitrogen physisorption, XRD, and NH(3)-TPD, in order to determine their morphological, crystallographic and chemical properties. Slight desilication phenomena were observed using hydroxides as precursors, whereas the treatment with Cs salts lead to higher crystallinity losses. Several successive adsorption-desorption cycles were carried out in order to check the regenerability of the adsorbents. Cesium-treated zeolites present higher carbon dioxide retention capacities than the sodium treated and than the parent material. When working with these Cs-modified materials, the desorption takes place mainly at temperatures between 250 and 400 degrees C, results of great practical interest, since it allows the use these kinds of materials for adsorption-desorption cycles. The evolution of the retention capacity with temperature is also markedly more positive for Cs-treated zeolite, especially when carbonate is used as the precursor. These materials maintain high retention capacities at 100 degrees C (10mg g(-1)) and even at 200 degrees C (3mg g(-1)), temperatures at which the most of the adsorbents are inactive.