Direct N2O decomposition over La2NiO4-based perovskite-type oxides

Direct decomposition of N₂O by perovskite-structure catalysts including La₂NiO₄, LaSrNiO₄, and La_0.7Ce_0.3SrNiO₄ was investigated. The catalysts were prepared by the Pechini method and characterized by x-ray diffraction (XRD), BET, scanning electron microscopy (SEM), and O₂-TPD. Experimental results indicate that the properties of La₂NiO₄ are significantly improved by partially substituting La with Sr and Ce. N₂O decomposition efficiencies achieved with LaSrNiO₄ and La_0.7Ce_0.3SrNiO₄ are 44 and 36%, respectively, at 400ºC. As the temperature was increased to 600ºC, N₂O decomposition efficiency achieved with LaSrNiO₄ and La_0.7Ce_0.3SrNiO₄ reached 100% at an inlet N₂O concentration of 1,000 ppm, while the space velocity was fixed at 8,000 hr^?1. In addition, effects of various parameters including oxygen, water vapor, and space velocity were also explored. The results indicate that N₂O decomposition efficiencies achieved with LaSrNiO₄ and La_0.7Ce_0.3SrNiO₄ are not significantly affected as space velocity is increased from 8,000 to 20,000 hr^?1, while La_0.7Ce_0.3SrNiO₄ shows better tolerance for O₂ and H₂O_(g). On the other hand, N₂ yield with LaSrNiO₄ as catalyst can be significantly improved by doping Ce. At a gas hour space velocity of 8,000 hr^?1, and a temperature of 600ºC, high N₂O decomposition efficiency and N₂ yield were maintained throughout the durability test of 60 hr, indicating the long-term stability of La_0.7Ce_0.3SrNiO₄ for N₂O decomposition.

Implications:Nitrous oxide (N₂O) not only has a high global warming potential (GWP₁₀₀ = 310), but also potentially destroys ozone in the stratosphere. Pervoskite-type catalysts including La₂NiO₄, LaSrNiO₄, and La_0.7Ce_0.3SrNiO₄ are applied for direct N₂O decomposition. The results show that N₂O decomposition can be enhanced as Sr and Ce are doped into La₂NiO₄. At 600ºC, N₂O decomposition efficiencies achieved with LaSrNiO₄ and La_0.7Ce_0.3SrNiO₄ reach 100%, demonstrating high activity and good potential for direct N₂O decomposition. Effects of O₂ and H₂O_(g) contents on catalytic activities are also evaluated and discussed.     

Extending the environmental risk assessment for oseltamivir (Tamiflu®) under pandemic use conditions to the coastal marine compartment

In case of an avian-influenza-derived human flu pandemic, an inordinately high use of medicines over several weeks is predicted, in particular for the recommended influenza antiviral oseltamivir (Tamiflu). While the risk of oseltamivir to sewage works and freshwater bodies has already been assessed, the fact that a large percentage of the human population worldwide lives relatively close to the sea raises concern for its environmental compatibility in coastal marine waters. The potential risk of high oseltamivir use to the marine compartment is assessed in this publication, based on the 2003 European Community Technical Guidance Document (TGD) for risk assessment. Subchronic embryo–larval ecotoxicity tests with three marine invertebrates (Pomatoceros triqueter, Annelida; Mytilus edulis, Mollusca; Paracentrotus lividus, Echinodermata) and chronic growth inhibition tests with two different groups of marine microalgae (Isochrysis galbana, Haptophyta; Skeletonema costatum, Heterokontophyta) were performed with the active substance oseltamivir carboxylic acid to derive a dependable marine predicted no-effect concentration (PNEC). This was compared to a predicted environmental concentration (PEC) for oseltamivir in coastal waters, based on the worst-case freshwater PEC. The PEC/PNEC risk characterisation ratio for the marine compartment is well below 1, which in the terminology of the TGD signifies no immediate concern. Further, while oseltamivir may be persistent (P), it is not bioaccumulative (B) nor highly ecotoxic (T) and therefore not a PBT substance. In conclusion, even a high pandemic use of oseltamivir would not lead to a significant risk for the marine compartment, in confirmation of the risk assessment for sewage works and freshwaters.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.     

Phytoremediation of a Petroleum‐Hydrocarbon Contaminated Shallow Aquifer in Elizabeth City,North Carolina,USA

A former bulk fuel terminal in North Carolina is a groundwater phytoremediation demonstration site where 3,250 hybrid poplars, willows, and pine trees were planted from 2006 to 2008 over approximately 579,000 L of residual gasoline, diesel, and jet fuel. Since 2011, the groundwater altitude is lower in the area with trees than outside the planted area. Soil‐gas analyses showed a 95 percent mass loss for total petroleum hydrocarbons (TPH) and a 99 percent mass loss for benzene, toluene, ethylbenzene, and xylenes (BTEX). BTEX and methyl tert‐butyl ether concentrations have decreased in groundwater. Interpolations of free‐phase, fuel product gauging data show reduced thicknesses across the site and pooling of fuel product where poplar biomass is greatest. Isolated clusters of tree mortalities have persisted in areas with high TPH and BTEX mass. Toxicity assays showed impaired water use for willows and poplars exposed to the site's fuel product, but Populus survival was higher than the willows or pines on‐site, even in a noncontaminated control area. All four Populus clones survived well at the site. © 2014 Wiley Periodicals, Inc.*     

Impact of nano-CuO stress on rice (Oryza sativa L.) seedlings

Indiscriminate release of metal oxide nanoparticles (NPs) into the environment due to anthropogenic activities has become a serious threat to the ecological system including plants. The present study assesses the toxicity of nano-CuO on rice (Oryza sativa cv. Swarna) seedlings. Three different levels of stress (0.5 mM, 1.0 mM and 1.5 mM suspensions of copper II oxide, <50 nm particle size) were imposed and seedling growth performance was studied along control at 7 and 14 d of experiment. Modulation of ascorbate–glutathione cycle, membrane damage, in vivo ROS detection, foliar H₂O₂ and proline accumulation under nano-CuO stress were investigated in detail to get an overview of nano-stress response of rice. Seed germination percentage was significantly reduced under stress. Higher uptake of Evans blue by nano-CuO stressed roots over control indicates loss of root cells viability. Presence of dark blue and deep brown spots on leaves evident after histochemical staining with NBT and DAB respectively indicate severe oxidative burst under nano-copper stress. APX activity was found to be significantly increased in 1.0 and 1.5 mM CuO treatments. Nevertheless, elevated APX activity might be insufficient to scavenge all H₂O₂ produced in excess under nano-CuO stress. That may be the reason why stressed leaves accumulated significantly higher H₂O₂ instead of having enhanced APX activity. In addition, increased GR activity coupled with isolated increase in GSH/GSSG ratio does not seem to prevent cells from oxidative damages, as evident from higher MDA level in leaves of nano-CuO stressed seedlings over control. Enhanced proline accumulation also does not give much protection against nano-CuO stress. Decline in carotenoids level might be another determining factor of meager performance of rice seedlings in combating nano-CuO stress induced oxidative damages.     

A storm event-based approach to TMDL development

It is vitally important to define the critical condition for a receiving water body in the total maximum daily load (TMDL) development process. One of the major disadvantages of using a continuous simulation approach is that there is no guarantee that the most critical condition will be covered within the subjectively selected representative hydrologic period, which is usually several years depending on the availability of data. Another limitation of the continuous simulation approach, compared to a design storm approach, is the lack of an estimate of the risk involved. Because of the above limitations, a storm event-based critical flow-storm (CFS) approach was previously developed to explicitly address the critical condition as a combination of a prescribed stream flow and a storm event of certain magnitude, both having a certain frequency of occurrence and when combined, would create a critical condition. The CFS approach was tested successfully in a TMDL study for Muddy Creek in Virginia. The present paper reports results of a comparative study on the applicability of the CFS approach in Taiwan. The Dy-yu creek watershed in northern Taiwan differs significantly from Muddy Creek in terms of climate, hydrology, terrain, and other characteristics. Results show that the critical condition for different watersheds might be also different, and that the CFS approach could clearly define that critical condition and should be considered as an alternative method for TMDL development to a continuous simulation approach.     

N-nitrosodimethylamine and trihalomethane formation and minimisation in Southeast Queensland drinking water

This study assesses the prevalence of disinfection by-product (DBP) precursors in some Southeast Queensland drinking water sources by conducting formation potential experiments for the four regulated trihalomethanes (THMs), and the potent carcinogen, N-nitrosodimethylamine (NDMA). NDMA formation potentials were consistently low (<5-21 ng/L), and total THM (tTHM) formation potentials were consistently below the Australian Drinking Water Guideline (250 μg/L). NDMA concentration of finished drinking waters was also monitored and found to be <5 ng/L in all cases. The effect of coagulation and advanced oxidation on the formation of NDMA and THMs is also reported. UV/H(2)O(2) pre-treatment was effective in producing water with very low THMs concentrations, and UV irradiation was an effective method for NDMA degradation. H(2)O(2) was not required for the observed NDMA degradation to occur. Coagulation using alum, ferric chloride or poly(diallyldimethylammonium chloride) (polyDADMAC) was ineffective in removing DBPs precursors from the source water studied, irrespective of the low dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) attained. Rather, coagulation with polyDADMAC caused an increase in NDMA formation potential upon chloramination, and all coagulants led to an increased tTHM formation potential upon chlorination due to the high bromide concentration of the source water studied.     

Development of a multi-criteria index ranking system for urban runoff best management practices (BMPs) selection

Low impact development best management practices (LID-BMPs) are considered to be cost-effective measures for mitigating the water quantity and quality impact of urban runoff. Currently, there are many types of LID-BMPs, and each type has its own intrinsic technical and/or economical characteristics and limitations for implementation. The selection of the most appropriate BMP type(s) for a specific installation site is therefore a very important planning step. In the present study, a multi-criteria selection index system (MCIS) for LID-BMP planning was developed. The selection indexes include 12 first-level indices and 26 second-level indices which reflect the specific installation site characteristics pertaining to site suitability, runoff control performance, and economics of implementation. A mechanism for ranking the BMPs was devised. First, each individual second-level index was assigned a numeric value that was based on site characteristics and information on LID-BMPs. The quantified indices were normalized and then integrated to obtain the score for each of the first-level index. The final evaluation scores of each LID-BMP were then calculated based on the scores for the first-level indices. Finally, the appropriate BMP types for a specific installation site were determined according to the rank of the final evaluation scores. In order to facilitate the application of the MCIS BMP ranking system, the computational process has been coded into a software program, BMPSELEC. A case study demonstrating the MCIS methodology, using an LID-BMP implementation planning at a college campus in Foshan, Guangdong Province, is presented.     

Geographic distribution and environmental characterization of livestock production systems in Eastern Africa

The central role played by livestock in the livelihoods of rural households in the developing world is seldom fully appreciated by policy makers, development agencies and donors. Knowledge gaps in the geographic distribution and environmental determinants of farming systems, especially if viewed through the livestock lens, compound this problem. We have produced a map of pastoral, agro-pastoral and mixed farming systems across Eastern Africa, by analysing datasets collected in the framework of livelihood analysis. Input data were gathered between 2000 and 2007 by various emergency and development agencies for Djibouti, Eritrea, Kenya, Somalia, Uganda and parts of Ethiopia and Sudan. A quantitative definition of the production systems is adopted, based on the ratio of livestock- to crop-derived income. The resulting livelihood-based map of livestock production systems was compared through correspondence analysis to an alternative livestock production systems map, produced independently from environmental data. Convergence between the two mapping approaches was evident. The geographic distribution of the livestock production systems was also modelled using multivariate analysis of remotely sensed and other geospatial datasets. Models show high statistical accuracy, and were thus used to fill the gaps in the observed distribution of livestock production systems. Finally, selected environmental factors underpinning the systems (agro-climatology, human and livestock populations and land cover) were analysed in detail, enabling the livestock production systems to be characterized in terms of them. The regional scope of the map, as well as its direct link with a vast amount of livelihood information, render it a valuable tool for a range of development and research applications, including those related to global change.     

A WATER QUALITY‐BASED APPROACH FOR WATERSHED WIDE BMP STRATEGIES1

ABSTRACT: Watershed management strategies generally involve controlling nonpoint source pollution by implementing various best management practices (BMPs). Currently, stormwater management programs in most states use a performance‐based approach to implement onsite BMPs. This approach fails to link the onsite BMP performance directly to receiving water quality benefits, and it does not take into account the combined treatment effects of all the stormwater management practices within a watershed. To address these issues, this paper proposes a water quality‐based BMP planning approach for effective nonpoint source pollution control at a watershed scale. A coupled modeling system consisting of a watershed model (HSPF) and a receiving water quality model (CE‐QUAL‐W2) was developed to establish the linkage between BMP performance and receiving water quality targets. A Monte Carlo simulation approach was utilized to develop alternative BMP strategies at a watershed level. The developed methodology was applied to the Swift Creek Reservoir watershed in Virginia, and the results show that the proposed approach allows for the development of BMP strategies that lead to full compliance with water quality requirements.