A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.     

Accelerated seeded precipitation pre-treatment of municipal wastewater to reduce scaling

Membrane based treatment processes are very effective in removing salt from wastewater, but are hindered by calcium scale deposit formation. This study investigates the feasibility of removing calcium from treated sewage wastewater using accelerated seeded precipitation. The rate of calcium removal was measured during bench scale batch mode seeded precipitation experiments at pH 9.5 using various quantities of calcium carbonate as seed material. The results indicate that accelerated seeded precipitation may be a feasible option for the decrease of calcium in reverse osmosis concentrate streams during the desalination of treated sewage wastewater for irrigation purposes, promising decreased incidence of scaling and the option to control the sodium adsorption ratio and nutritional properties of the desalted water. It was found that accelerated seeded precipitation of calcium from treated sewage wastewater was largely ineffective if carried out without pre-treatment of the wastewater. Evidence was presented that suggests that phosphate may be a major interfering substance for the seeded precipitation of calcium from this type of wastewater. A pH adjustment to 9.5 followed by a 1-h equilibration period was found to be an effective pre-treatment for the removal of interferences. Calcium carbonate seed addition at 10 g l⁻¹ to wastewater that had been pre-treated in this way was found to result in calcium precipitation from supersaturated level at 60 mg l⁻¹ to saturated level at 5 mg l⁻¹. Approximately 90% reduction of the calcium level occurred 5 min after seed addition. A further 10% reduction was achieved 30 min after seed addition.     

Spatiotemporal Associations of Reservoir Nutrient Characteristics and the Invasive,Harmful Alga Prymnesium parvum in West Texas

Golden alga (Prymnesium parvum) is a harmful alga that has caused ecological and economic harm in freshwater and marine systems worldwide. In inland systems of North America, toxic blooms have nearly eliminated fish populations in some systems. Modifying nutrient profiles through alterations to land or water use may be a viable alternative for golden alga control in reservoirs. The main objective of this study was to improve our understanding of the nutrient dynamics that influence golden alga bloom formation and toxicity in west Texas reservoirs. We examined eight sites in the Upper Colorado River basin, Texas: three impacted reservoirs that have experienced repeated golden alga blooms; two reference reservoirs where golden alga is present but nontoxic; and three confluence sites downstream of the impacted and reference sites. Total, inorganic, and organic nitrogen and phosphorus and their ratios were quantified monthly along with golden alga abundance and ichthyotoxicity between December 2010 and July 2011. Blooms persisted for several months at the impacted sites, which were characterized by high organic nitrogen and low inorganic nitrogen. At impacted sites, abundance was positively associated with inorganic phosphorus and bloom termination coincided with increases in inorganic nitrogen and decreases in inorganic phosphorus in late spring. Management of both inorganic and organic forms of nutrients may create conditions in reservoirs unfavorable to golden alga.     

Calibrating a Basin‐Scale Groundwater Model to Remotely Sensed Estimates of Groundwater Evapotranspiration

Remotely sensed vegetation indices correspond to canopy vigor and cover and have been successfully used to estimate groundwater evapotranspiration (ET_g) over large spatial and temporal scales. However, these data do not provide information on depth to groundwater (dtgw) necessary for groundwater models (GWM) to calculate ET_g. An iterative approach is provided that calibrates GWM to ET_g derived from Landsat estimates of the Enhanced Vegetation Index (EVI). The approach is applied to different vegetation groups in Mason Valley, Nevada over an 11‐year time span. An uncertainty analysis is done to estimate the resulting mean and 90% confidence intervals in ET_g to dtgw relationships to quantify errors associated with plant physiologic complexity, species variability, and parameter smoothing to the 100 m GWM‐grid, temporal variability in soil moisture and nonuniqueness in the solution. Additionally, a first‐order second moment analysis shows ET_g to dtgw relationships are almost exclusively sensitive to estimated land surface, or maximum, ET_g despite relatively large uncertainty in extinction depths and hydraulic conductivity. The EVI method of estimating ET_g appears to bias ET_g during years with exceptionally wet spring/summer conditions. Excluding these years improves model performance significantly but highlights the need to develop a methodology that accounts not only on quantity but timing of annual precipitation on phreatophyte greenness.     

Influence of uncertain reaction rates on ozone sensitivity to emissions

Air quality models rely upon simplified photochemical mechanisms to efficiently represent the thousands of chemical species that interact to form air pollution. Uncertainties in the chemical reaction rate constants and photolysis frequencies that comprise those mechanisms can generate uncertainty in the estimation of pollutant concentrations and their responsiveness to emission controls. A high-order sensitivity analysis technique is applied to quantify the extent to which reaction rate uncertainties influence estimates of ozone concentrations and their sensitivities to precursor emissions during an air pollution episode in Houston, Texas. Several reactions were found to have much larger proportional effects on ozone’s sensitivities to emissions than on its concentrations. In particular, uncertainties in photolysis frequencies and in the rate of reaction between NO₂ and OH to form nitric acid can significantly influence the magnitude and sign of peak ozone sensitivity to nitrogen oxide (NO_x) emissions. Ozone sensitivity to VOCs exhibits a much more muted response to uncertainties in the reaction rate constants and photolysis frequencies considered here. The results indicate the importance of accurate reaction rate constants to predicting the ozone impacts resulting from NO_x emission controls.     

Demographic Forecasting in Koala Conservation

Abstract: The koala currently needs conservation intervention. There is clear evidence of decline in many populations, but the existence of other stable or expanding populations offers the possibility of a variety of creative solutions to their conservation problems. The 1998 National Koala Conservation Strategy emphasizes the need to obtain demographic information and to use this information to assess management options for koalas. We need accurate diagnoses of the status of koala populations and forecasts of their demographic future with and without particular management actions. In a qualitative fashion, this process has been undertaken many times on a local and national scale. Quantitative demographic forecasting tools are increasingly available, and koala management could benefit from their application both at the scale of individual populations and more broadly. There is already a considerable body of suitable data on the dispersal, effects of normal and catastrophic environmental variation on reproduction and survival, and on the effects of habitat change. Demographic forecasting, however, is hampered because the full suite of information is rarely available from a single population. In two Queensland populations, retrospective population viability analyses provided forecasts that were in agreement with observed population trends. Work is needed to determine whether data from one population can be applied to other populations. Models can then be developed to make projections at a multipopulation level on the basis of local population dynamics and dispersal. Certain koala populations, because of their long history of study, offer the opportunity to test demographic models retrospectively. These tests will not only aid in fine-tuning the models for koala biology and data but will also assist with the more general process of validating the models.     

Evaluation of ion exchange resins for the removal of dissolved organic matter from biologically treated paper mill effluent

In this study, the efficiency of six ion exchange resins to reduce the dissolved organic matter (DOM) from a biologically treated newsprint mill effluent was evaluated and the dominant removal mechanism of residual organics was established using advanced organic characterisations techniques. Among the resins screened, TAN1 possessed favourable Freundlich parameters, high resin capacity and solute affinity, closely followed by Marathon MSA and Marathon WBA. The removal efficiency of colour and lignin residuals was generally good for the anion exchange resins, greater than 50% and 75% respectively. In terms of the DOM fractions removal measured through liquid chromatography–organic carbon and nitrogen detector (LC–OCND), the resins mainly targeted the removal of humic and fulvic acids of molecular weight ranging between 500 and 1000 g mol^?1, the portion expected to contribute the most to the aromaticity of the effluent. For the anion exchange resins, physical adsorption operated along with ion exchange mechanism assisting to remove neutral and transphilic acid fractions of DOM. The column studies confirmed TAN1 being the best of those screened, exhibited the longest mass transfer zone and maximum treatable volume of effluent. The treatable effluent volume with 50% reduction in dissolved organic carbon (DOC) was 4.8 L for TAN1 followed by Marathon MSA – 3.6 L, Marathon 11 – 2.0 L, 21K-XLT – 1.5 L and Marathon WBA – 1.2 L. The cation exchange resin G26 was not effective in DOM removal as the maximum DOC removal obtained was only 27%. The resin capacity could not be completely restored for any of the resins; however, a maximum restoration up to 74% and 93% was achieved for TAN1 and Marathon WBA resins. While this feasibility study indicates the potential option of using ion exchange resins for the reclamation of paper mill effluent, the need for improving the regeneration protocols to restore the resin efficiency is also identified. Similarly, care should be taken while employing LC–OCND for characterising resin-treated effluents, as the resin degradation is expected to contribute some organic carbon moieties misleading the actual performance of resin.