South Pole Antarctica observations and modeling results: New insights on HOx radical and sulfur chemistry

Measurements of OH, H₂SO₄, and MSA at South Pole (SP) Antarctica were recorded as a part of the 2003 Antarctic Chemistry Investigation (ANTCI 2003). The time period 22 November, 2003–2 January, 2004 provided a unique opportunity to observe atmospheric chemistry at SP under both natural conditions as well as those uniquely defined by a solar eclipse event. Results under natural solar conditions generally confirmed those reported previously in the year 2000. In both years the major chemical driver leading to large scale fluctuations in OH was shifts in the concentration levels of NO. Like in 2000, however, the 2003 observational data were systematically lower than model predictions. This can be interpreted as indicating that the model mechanism is still missing a significant HO_x sink reaction(s); or, alternatively, that the OH calibration source may have problems. Still a final possibility could involve the integrity of the OH sampling scheme which involved a fixed building site. As expected, during the peak in the solar eclipse both NO and OH showed large decreases in their respective concentrations. Interestingly, the observational OH profile could only be approximated by the model mechanism upon adding an additional HO_x radical source in the form of snow emissions of CH₂O and/or H₂O₂. This would lead one to think that either CH₂O and/or H₂O₂ snow emissions represent a significant HO_x radical source under summertime conditions at SP. Observations of H₂SO₄ and MSA revealed both species to be present at very low concentrations (e.g., 5 × 10⁵ and 1 × 10⁵ molec cm^?3, respectively), but similar to those reported in 2000. The first measurements of SO₂ at SP demonstrated a close coupling with the oxidation product H₂SO₄. The observed low concentrations of MSA appear to be counter to the most recent thinking by glacio-chemists who have suggested that the plateau's lower atmosphere should have elevated levels of MSA. We speculate here that the absence of MSA may reflect efficient atmospheric removal mechanisms for this species involving either dynamical and/or chemical processes.     

Establishing ozone flux–response relationships for winter wheat: Analysis of uncertainties based on data for UK and Polish genotypes

The work outlined in this paper had three objectives. The first was to explore the effects of ozone pollution on grain yield and quality of commercially-grown winter wheat cultivars. The second was to derive a stomatal ozone flux model for winter wheat and compare with those already developed for spring wheat. The third was to evaluate exposure- versus flux–response approaches from a risk assessment perspective, and explore the implications of genetic variation in modelled ozone flux.Fifteen winter wheat cultivars were grown in open-top chambers where they were exposed to four levels of ozone. During fumigation, stomatal conductance measurements were made over the lifespan of the flag leaf across a range of environmental conditions. Although significant intra-specific variation in ‘ozone sensitivity’ (in terms of impacts on yield) was identified, yield was inversely related (R² = 0.63, P < 0.001) to the accumulated hourly averaged ozone exposure above 40 ppb during daylight hours (AOT40) across the dataset. The adverse effect of ozone on yield was principally due to a decline in seed weight. Algorithms defining the influence of environmental variables on stomatal uptake were subtly different from those currently in use, based on data for spring wheat, to map ozone impacts on pan-European cereal yield. Considerable intra-specific variation in phenological effects was identified. This meant that an ‘average behaviour’ had to be derived which reduced the predictive capability of the derived stomatal flux model (R² = 0.49, P < 0.001, 15 cultivars included). Indeed, given the intra-specific variability encountered, the flux model that was derived from the full dataset was no better in predicting O₃ impacts on wheat yield than was the AOT40 index. The study highlights the need to use ozone risk assessment tools appropriate to specific vegetation types when modelling and mapping ozone impacts at the regional level.     

Analytical Solutions to the Linearized Boussinesq Equation for Assessing the Effects of Recharge on Aquifer Discharge1

Boggs, Kevin G., Robert W. Van Kirk, Gary S. Johnson, Jerry P. Fairley, and P. Steve Porter, 2010. Analytical Solutions to the Linearized Boussinesq Equation for Assessing the Effects of Recharge on Aquifer Discharge. Journal of the American Water Resources Association (JAWRA) 46(6):1116–1132. DOI: 10.1111/j.1752-1688.2010.00479.x Abstract: There is a need to develop a general understanding of how variations in aquifer recharge are reflected in discharge. Analytical solutions to the linearized Boussinesq equation governing flow in an unconfined aquifer provide a unified mathematical framework to quantify relationships among lag time, attenuation and distance between aquifer recharge and discharge and the effect of an up-gradient no-flow boundary. We applied this framework to three types of recharge: (1) instantaneous, (2) periodic, and (3) constant rate for a finite duration. When the temporal scale of recharge exceeds the diffusive aquifer time scale, recharge will be reflected in discharge quickly and with little attenuation. When aquifer time scale is large, most recharge events are shorter in scale than that of the aquifer, resulting in large attenuation. Attenuation is more sensitive to boundary effects than lag time, and boundary effects increase as recharge time scale increases. Boundary effects can often be ignored when the recharge source is farther than 1/3 of the domain length away from the no-flow boundary. We illustrate analytical results with application to the economically critical Eastern Snake River Plain Aquifer in Idaho. In this aquifer, detectable annual and decadal cycles in discharge can result from recharge no farther than 20 and 60 km away from the discharge point, respectively. The effects of more distant, long-term recharge can be detected only after a time lag of several decades.     

Emission factors for high-emitting vehicles based on on-road measurements of individual vehicle exhaust with a mobile measurement platform

Fuel-based emission factors for 143 light-duty gasoline vehicles (LDGVs) and 93 heavy-duty diesel trucks (HDDTs) were measured in Wilmington, CA using a zero-emission mobile measurement platform (MMP). The frequency distributions of emission factors of carbon monoxide (CO), nitrogen oxides (NO(x)), and particle mass with aerodynamic diameter below 2.5 microm (PM2.5) varied widely, whereas the average of the individual vehicle emission factors were comparable to those reported in previous tunnel and remote sensing studies as well as the predictions by Emission Factors (EMFAC) 2007 mobile source emission model for Los Angeles County. Variation in emissions due to different driving modes (idle, low- and high-speed acceleration, low- and high-speed cruise) was found to be relatively small in comparison to intervehicle variability and did not appear to interfere with the identification of high emitters, defined as the vehicles whose emissions were more than 5 times the fleet-average values. Using this definition, approximately 5% of the LDGVs and HDDTs measured were high emitters. Among the 143 LDGVs, the average emission factors of NO(x), black carbon (BC), PM2.5, and ultrafine particle (UFP) would be reduced by 34%, 39%, 44%, and 31%, respectively, by removing the highest 5% of emitting vehicles, whereas CO emission factor would be reduced by 50%. The emission distributions of the 93 HDDTs measured were even more skewed: approximately half of the NO(x) and CO fleet-average emission factors and more than 60% of PM2.5, UFP, and BC fleet-average emission factors would be reduced by eliminating the highest-emitting 5% HDDTs. Furthermore, high emissions of BC, PM2.5, and NO(x) tended to cluster among the same vehicles.     

Decolorization and detoxification of two textile industry effluents by the laccase/1-hydroxybenzotriazole system

The aim of this work was to determine the optimal conditions for the decolorization and the detoxification of two effluents from a textile industry—effluent A (the reactive dye bath Bezactive) and effluent B (the direct dye bath Tubantin)—using a laccase mediator system. Response surface methodology (RSM) was applied to optimize textile effluents decolorization. A Box–Behnken design using RSM with the four variables pH, effluent concentration, 1-hydroxybenzotriazole (HBT) concentration, and enzyme (laccase) concentration was used to determine correlations between the effects of these variables on the decolorization of the two effluents. The optimum conditions for pH and concentrations of HBT, effluent and laccase were 5, 1 mM, 50 % and 0.6 U/ml, respectively, for maximum decolorization of effluent A (68 %). For effluent B, optima were 4, 1 mM, 75 %, and 0.6 U/ml, respectively, for maximum decolorization of approximately 88 %. Both effluents were treated at 30 °C for 20 h. A quadratic model was obtained for each decolorization through this design. The experimental and predicted values were in good agreement and both models were highly significant. In addition, the toxicity of the two effluents was determined before and after laccase treatment using Saccharomyces cerevisiae, Bacillus cereus, and germination of tomato seeds.     

Assessing and testing prediction uncertainty for single tree-based models: A case study applied to northern hardwood stands in southern Québec, Canada

Estimating prediction uncertainty for a single tree-based model is hindered by the complex structure of these models. In this paper, we addressed this issue with a case study applied to northern hardwood stands in Québec, Canada. SaMARE is a stochastic single tree-based model that was designed for these types of stands. Using a Monte Carlo approach, the model can provide a mean predicted value and its confidence limits for some plot-level attributes.The mean predicted values were compared to observed values in terms of bias and accuracy. In addition to these common statistics, we compared nominal coverage of Monte Carlo-simulated confidence intervals with real (observed) coverage to verify the adequacy of the simulated uncertainty. A comparison was made using several plot-level attributes, which exhibited an increasing discriminative complexity. This complexity ranges from coarse attributes, such as all-species basal area, up to more complex ones, such as basal area for stems of a particular species and with sawlog potential.The results showed that in terms of absolute value, biases were small, but could be relatively high with respect to the average observed value when the discriminative complexity of the attribute increased. The comparison between nominal and real coverage of confidence intervals gave satisfactory results for all-species plot-level attributes. However, for some species-specific attributes, the Monte Carlo-simulated confidence intervals overestimated the real coverage.     

A free-enzyme catalyst for the bioremediation of environmental atrazine contamination

Herbicide contamination from agriculture is a major issue worldwide, and has been identified as a threat to freshwater and marine environments in the Great Barrier Reef World Heritage Area in Australia. The triazine herbicides are of particular concern because of potential adverse effects, both on photosynthetic organisms and upon vertebrate development. To date a number of bioremediation strategies have been proposed for triazine herbicides, but are unlikely to be implemented due to their reliance upon the release of genetically modified organisms. We propose an alternative strategy using a free-enzyme bioremediant, which is unconstrained by the issues surrounding the use of live organisms. Here we report an initial field trial with an enzyme-based product, demonstrating that the technology is technically capable of remediating water bodies contaminated with the most common triazine herbicide, atrazine.     

The use of silver as a selective precipitant for I in radioactive waste management

¹²⁹I is one of the more hazardous nuclides occurring in radioactive waste. In the form of I⁻, its most likely speciation, it is poorly sorbed on most geologic media. Several workers have suggested the use of silver to precipitate I⁻ as the insoluble AgI, in a cemented waste form, or as a “getter”. The efficacy of this procedure is examined by experiment, in conjunction with thermodynamic predictions.The addition of AgNO₃ to Portland cement leads to coprecipitation with C-S-H, with low Ag solubilities ( 10 μmg/L); 2–;3 orders of magnitude lower than predicted (from Ag₂O). AgI is stable in these matrices, with low aqueous I concentrations (<2 mg/L). In 85% BFS-15% OPC pastes, AgI is unstable due to redox and complexation reactions, with much I⁻ passing into solution; concentrations up to 900 mg/L were observed. It is shown that repository conditions, on closure, are also likely to induce solubilisation of I⁻ from AgI. It is concluded that the use of Ag is unlikely to significantly improve the immobilisation properties of the near field for radioiodine.