The occurrence, as well as the environmental fate and impact, of vegetable oil spills in freshwater wetlands have until now been unreported. Thus, the largest global vegetable oil spillage in a freshwater wetland, which occurred at the Con Joubert Bird Sanctuary wetland in 2007, presented an ideal opportunity to evaluate these impacts. Five post-spill sampling sites were selected within the wetland from which a variety of abiotic and biotic samples were collected bi-monthly over a period of 12 months. Abiotic variables included the sediment and water column oil concentrations, total nitrogen, total phosphorous, biochemical oxygen demand (BOD), silica, chlorophyll a, as well as in situ measurements of pH, electrical conductivity, and dissolved oxygen. Aquatic macroinvertebrates were chosen as biotic indicators in the study field due to their wide applicability as water quality indicators and were thus collected at each site. Spatial and temporal changes in total nitrogen, total phosphorous, and chlorophyll a concentrations as well as changes in pH were observed. The oil spillage also resulted in an increase in tolerant macroinvertebrate taxa, mainly Chironomidae and Psychodidae, at the sites closest to the source of the spillage. These two taxa, and to a lesser extent, Syrphidae, were identified as potentially useful indicators to determine the extent of vegetable oil contamination within a freshwater wetland. Furthermore, monitoring of these indicator taxa can be a useful management tool to determine the recovery of freshwater wetlands after vegetable oil spills. In the study, a static battery of bioassays of different biotic trophic levels was also employed to determine the adverse effects of the spilled vegetable oil on the biotic environment. It was evident from the result of the static battery of bioassay that adverse effects of the sunflower oil differ between trophic levels. The latter was in relationship with the data obtained from the field macroinvertebrate study, indicating that certain macroinvertebrate families were more tolerant to the adverse effects of sunflower oil than other families. © 2013 Springer Science+Business Media Dordrecht.

DayCent is a biogeochemical model of intermediate complexity widely used to simulate greenhouse gases (GHG), soil organic carbon and nutrients in crop, grassland, forest and savannah ecosystems. Although this model has been applied to a wide range of ecosystems, it is still typically parameterized through a traditional "trial and error" approach and has not been calibrated using statistical inverse modelling (i.e. algorithmic parameter estimation). The aim of this study is to establish and demonstrate a procedure for calibration of DayCent to improve estimation of GHG emissions. We coupled DayCent with the parameter estimation (PEST) software for inverse modelling. The PEST software can be used for calibration through regularized inversion as well as model sensitivity and uncertainty analysis. The DayCent model was analysed and calibrated using N2O flux data collected over 2 years at the Iowa State University Agronomy and Agricultural Engineering Research Farms, Boone, IA. Crop year 2003 data were used for model calibration and 2004 data were used for validation. The optimization of DayCent model parameters using PEST significantly reduced model residuals relative to the default DayCent parameter values. Parameter estimation improved the model performance by reducing the sum of weighted squared residual difference between measured and modelled outputs by up to 67 %. For the calibration period, simulation with the default model parameter values underestimated mean daily N2O flux by 98 %. After parameter estimation, the model underestimated the mean daily fluxes by 35 %. During the validation period, the calibrated model reduced sum of weighted squared residuals by 20 % relative to the default simulation. Sensitivity analysis performed provides important insights into the model structure providing guidance for model improvement. © 2013 Springer Science+Business Media Dordrecht.

Recent research on potential carcinogens in recreational waters has spawned public concerns about the long-term public health impacts of disinfectants used in pools. However, no attention has been given to the ecological and public health impacts of metal oxides in cosmetics and sunscreens within swimming pools where leisure activities occur. The discussion in this perspective focuses on the interaction between metal oxide nanoparticles released from swimmers into pools where algae is present, and the synergistic toxicological effects of pool algae adsorbed by metal oxide nanoparticles in the presence of disinfection byproducts in comparison to the absence of contaminants. This perspective will address research approaches to evaluating metal oxide nanoparticle impacts on pool algae, and the challenge of identifying the potential mechanisms leading to transformed algae.

Four room temperature ionic liquids, [BMIM][PF₆], [BMIM][NTf₂], [PEGMIM][PF₆], and Aliquat, were investigated regarding their use in a two-phase partition bioreactor dedicated to remove two hydrophobic VOC, dimethyldisulfide and toluene. Aliquat and [PEGMIM][PF₆] cannot be further considered, owing to the toxicity of the former shown during glucose uptake inhibition tests and the water solubility of the latter. The partition coefficients of [BMIM][PF₆] and [BMIM][NTf₂] were found comparable to those recorded for typical liquid solvents used in multiphase bioreactors. They were also non-biodegradable, showed during long-term biodegradability tests. After 1 day of lag time, similar glucose biodegradation rates were recorded in the presence of 5 % [BMIM][PF₆] or [BMIM][NTf₂], if compared to controls deprived of ionic liquid. However, a clear inhibitory effect of the ionic liquids was observed during VOC biodegradation experiments. This phenomenon was significantly minimized after acclimation of activated sludge to VOC, since nearly similar consumption rates of toluene were recorded in the control deprived of IL and in the presence of 5 % bmimPF₆, 0.49 and 0.48 g m⁻³ h⁻¹, respectively. These promising results showed that more complex acclimation strategies, including microbial acclimation to both ionic liquids and VOC, will have to be considered.

Data on the influence of substrate composition on the anaerobic degradation of peptone in a bench-scale packed-bed reactor are presented and discussed. The experiments were conducted in a horizontal-flow anaerobic immobilised biomass reactor operated with a hydraulic detention time of 4 h. Peptone was the sole carbon source in the first experiment (E1). In the second experiment (E2), the reactor was fed with peptone and carbohydrates, and in the third experiment (E3), lipids were also added. At end of each experiment, the samples were collected to obtain spatial profiles of the substrates and intermediary metabolites. A modified first-order kinetic expression fits well with the chemical oxygen demand data, allowing kinetic parameter inference in both E1 and E2. The presence of lipids in the E3 influent clearly disturbed the equilibrium of the process, which could be better represented by two first-order kinetic expressions in series. A kinetic model of irreversible first-order reactions (in series and in parallel) with two intermediate products was proposed for representing the entire process. Several modifications of the metabolic routes were clearly represented by the values of the model parameters. It was also possible to conclude that the adsorption of lipids in the fixed bed caused a decrease in the consumption rate of proteins and acetate. Microscopy examinations and fluorescence in situ hybridisation analyses corroborated the conclusions from the kinetic study. The frequencies of the microorganisms changed as the substrate composition was modified, indicating the capability of the microorganisms to adapt.

Inorganic forms of mercury (Hg) can be converted by natural processes into methylmercury, a highly potent neurotoxin that can bioaccumulate in food chains and pose a risk to human health. Although Hg can enter aquatic environments through direct deposition, the predominant source derives from complex terrestrial cycling in nearby ecosystem vegetation and soils. Here we assess the spatial distribution of soil and litterfall Hg within two paired catchments of the Shenandoah National Park: the northwest-facing North Fork Dry Run (NFDR) and the southeast-facing Hannah Run (HR) catchments. Litterfall Hg concentrations were not significantly different between the NFDR and HR catchments. This may be attributable to the speciation of Hg (gaseous elemental Hg) that is involved in leaf-level accumulation. Significant differences in soil organic-layer Hg concentrations were observed between the two study catchments, with NFDR soils having roughly 50 % higher Hg concentrations than those from HR. These differences can be explained by differences in soil N content (and to a lesser extent soil C content) between catchments, as both elements exert a strong control of the amount of Hg bound in soils. We found no evidence that topographic aspect contributes to the spatial variability of soil Hg concentrations in these paired catchments, but did detect an influence from elevation. Soils located near ridges in mountainous catchments can contain relatively high Hg concentrations due to (1) lower turnover rates in soil organic matter pools, (2) enhanced deposition, and (3) limited mobilization of Hg from those areas.

The present paper examines the phosphate adsorption from aqueous solutions onto goethite, bentonite, and bentonite–goethite system. The properties of the materials were studied by X-ray diffraction (XRD), attenuated total reflectance (ATR), and NMR spectra and by the measurement of the specific surface area, the point of zero charge (p.z.c.) and the pore-specific volume. ATR and NMR spectra of bentonite and bentonite–goethite system show peaks which correspond to tetrahedrally and octahedrally coordinated Al. The specific surface area of the system differs according to the appropriate method used, while system’s p.z.c. is higher than bentonite and lower than goethite. The pore-specific volume of bentonite–goethite system is higher than that of bentonite or goethite. According to XRD spectrum of bentonite–goethite system, goethite coats the (001) spacing of bentonite while the coating of (010) plane of bentonite is limited. The crystallinity of the system decreases and the negative permanent charge increases. Phosphate adsorption experiments took place at different pH (3.8–9.0) and concentrations (40.3–443.5 μmol L⁻¹) and constant capacitance model was applied to describe adsorption. A ligand exchange mechanism characterizes the model because the charge is divided among adsorbate and adsorbent. The constant capacitance model describes the adsorption mechanism in all examined pH. This model can be utilized in such systems using the surface protonation-dissociation constant of goethite and showing the exact shape of the adsorption isotherms for different pH values. Τhe produced low-cost bentonite–goethite system presents the highest adsorption of P per kilogram of goethite.

Because of the existence of a semi-analytical solution, the Henry saltwater intrusion problem has been widely used for benchmarking non-reactive density-driven flow models. In this work, we extend the semi-analytical solution of Henry to reactive transport in variable-density fluid flow. Accurate semi-analytical solutions are provided for three test cases dealing with saltwater transport including dissolution and degradation reactions. About 6,195 terms are required in the Fourier series to obtain a stable solution for these test cases instead of the 78 initially used by Henry (Sea Water in Coastal Aquifers 1613-C:70–84, 1964) for the non-reactive problem. The resolution of the highly non-linear system is made possible due to the modified Powell hybrid algorithm with an analytical evaluation of the Jacobian. Numerical simulations are performed using different numerical methods and grid sizes to evaluate the benefits of these new test cases for benchmarking reactive density-driven flow models.

Arrival of tar balls to the Goa coast during pre- and southwest monsoon seasons has been a regular phenomenon in the past few years. In one such event, we observed tar ball deposits along the Goa coast during August 2010, April 2011 and May 2011 when no oil spill was reported in the Arabian Sea (AS). The only source for the formation of tar balls could be the spill/tanker-wash from the tankers passing through the international tanker routes across the AS. Assuming this, an attempt has been made to simulate surface winds, currents and tar ball trajectories for August 2010 using hydrodynamics and particle tracking models. Tar ball particles were released numerically at eight locations in the AS, and five of them reached the Goa coast, matching reasonably well with the observations. The present study confirms our view that the source of these tar balls is the accidental spills or tanker-wash along the international oil tanker route in the AS. A review of the global scenario of tar ball study is also presented in the Introduction.

Nanoscaled Bi₂O₃ particles coated on ZnO nanorods (ZNRs) have been fabricated by combining hydrothermal technique with a chemical precipitation method. X-ray diffraction, field emission-scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and UV–vis absorption and photoluminescence studies were adapted to characterize the structure, morphologies, and optical properties of the nanocomposites. The results indicated that small Bi₂O₃ nanoparticles were well distributed on the surfaces of ZNRs. And the Bi₂O₃–ZNR nanocomposites showed high charge separation efficiency and •OH generation ability as evidenced by photoluminescence spectra. Under irradiation of a 55-W compact fluorescent lamp, the Bi₂O₃–ZNR nanocomposites demonstrated photocatalytic activities higher than pure ZNRs in the degradation of two endocrine-disrupting chemicals, phenol and methylparaben, which might be attributed to the high separation efficiency of photogenerated electron–hole pairs based on the cooperative role of Bi₂O₃ loading on ZNRs. Moreover, the Bi₂O₃–ZNR nanocomposite could be easily recovered and reused due to their one-dimensional nanostructural property. All these characteristics brought enormous benefits of Bi₂O₃–ZNR nanocomposites to the practical application in indoor environmental remediation.