Formation of a ternary neptunyl(V) biscarbonato inner-sphere sorption complex inhibits calcite growth rate

Neptunyl, Np(V)O(2)(+), along with the other actinyl ions U(VI)O(2)(2+) and Pu(V,VI)O(2)((+,2+)), is considered to be highly mobile in the geosphere, while interaction with mineral surfaces (inner- or outer-sphere adsorption, ion-exchange, and coprecipitation/structural incorporation) may retard its migration. Detailed information about the exact interaction mechanisms including the structure and stoichiometry of the adsorption complexes is crucial to predict the retention behavior in diverse geochemical environments. Here, we investigated the structure of the neptunyl adsorption complex at the calcite-water interface at pH 8.3 in equilibrium with air by means of low-temperature (15K) EXAFS spectroscopy at the Np-L(III) edge. The coordination environment of neptunyl consists of two axial oxygen atoms at 1.87(±0.01)?, and an equatorial oxygen shell of six atoms at 2.51(±0.01)?. Two oxygen backscatterers at 3.50(±0.04)? along with calcium backscatterers at 3.95(±0.03)? suggest that neptunyl is linked to the calcite surface through two monodentate bonds towards carbonate groups of the calcite surface. Two additional carbon backscatterers at 2.94(±0.02)? are attributed to two carbonate ions in bidentate coordination. This structural environment is conclusively interpreted as a ternary surface complex, where a neptunyl biscarbonato complex sorbs through two monodentate carbonate bonds to steps at the calcite (104) face, while the two bidentately coordinated carbonate groups point away from the surface. This structural information is further supported by Mixed Flow Reactor (MFR) experiments. They show a significant decrease of the calcite growth rate in the presence of neptunyl(V), in line with blockage of the most active crystal growth sites, step and kink sites, by adsorption of neptunyl. Formation of this sorption complex constitutes an important retention mechanism for neptunyl in calcite-rich environments.     

Applying Zonation Methods and Tabu Search to Improve the Ground‐Water Modeling1

Abstract: An optimization procedure combining zonation methods with the Tabu Search method is proposed to identify the spatial distribution of hydraulic conductivity field. Three zonation methods, Voronoi diagram (VD), multiplicatively weighted Voronoi diagram (MWVD), and pattern zonation are adopted for the parameterization purposes. With the consideration of the homogeneity and the heterogeneity, there are four spatial distributions of hydraulic conductivity designed to test whether the parameter structure can be successfully identified. The fitting residual error is first considered to determine an adequate number of zones without over parameterization. Then, the parameter uncertainty is evaluated the decision of the number of zones. The results indicate that the MWVD performs better than other two methods because the MWVD has better flexibility in describing the zonal boundaries with small number of decision variables.     

Production of polyhydroxyalkanoate during treatment of tomato cannery wastewater.

Polyhydroxyalkanoate (PHA) production was achieved using tomato cannery waste coupled with a mixed microbial culture during wastewater treatment. The two-stage PHA production process comprised a sequencing batch reactor (SBR), operating under a periodic feast-famine regime, to accomplish simultaneously wastewater treatment and selection of PHA-accumulating microbes, followed by a batch reactor for the production of PHA-rich biomass. The SBRs were efficient at removing soluble carbon (84%), ammonia (100%), and phosphorus (76%). Meanwhile, PHA-accumulating microbes were enriched under the SBR operating conditions, and PHA content on a cell-weight basis was within the range 7 to 11% in nonfiltered wastewater and 2 to 8% in filtered wastewater. Subsequently, batch studies were implemented with varying loading rates, ranging from 0.4 to 3.2 food-to-microorganism ratios. A maximum 20% PHA content on a cell-weight basis was obtained. Based on the experimental results, a PHA biosynthesis-degradation kinetic model was developed to (1) aid in the design of a pilot- or full-scale PHA production process coupled with wastewater treatment and (2) determine optimal conditions for harvest of PHA-rich biomass.     

Environmental risks of farmed and barren alkaline coal ash landfills in Tuzla, Bosnia and Herzegovina

The disposal of coal combustion residues (CCR) has led to a significant consumption of land in the West Balkan region. In Tuzla (Bosnia and Herzegovina) we studied previously soil-covered (farmed) and barren CCR landfills including management practises, field ageing of CCR and the transfer of trace elements into crops, wild plants and wastewaters. Soil tillage resulted in mixing of cover soil with CCR. Medicago sativa showed very low Cu:Mo ratios (1.25) which may cause hypocuprosis in ruminants. Total loads of inorganic pollutants in the CCR transport water, but not pH ( approximately 12), were below regulatory limits of most EU countries. Arsenic concentrations in CCR transport water were <2microgl(-1) whereas reductive conditions in an abandoned landfill significantly enhanced concentrations in leachates (44microgl(-1)). The opposite pattern was found for Cr likely due to large initial leaching of CrVI. Public use of landfills, including farming, should be based on a prior risk assessment due to the heterogeneity of CCR.     

Ammonia in the environment: from ancient times to the present

Recent research on atmospheric ammonia has made good progress in quantifying sources/sinks and environmental impacts. This paper reviews the achievements and places them in their historical context. It considers the role of ammonia in the development of agricultural science and air chemistry, showing how these arose out of foundations in 18th century chemistry and medieval alchemy, and then identifies the original environmental sources from which the ancients obtained ammonia. Ammonia is revealed as a compound of key human interest through the centuries, with a central role played by sal ammoniac in alchemy and the emergence of modern science. The review highlights how recent environmental research has emphasized volatilization sources of ammonia. Conversely, the historical records emphasize the role of high-temperature sources, including dung burning, coal burning, naturally burning coal seams and volcanoes. Present estimates of ammonia emissions from these sources are based on few measurements, which should be a future priority.     

Environmental innovation activities and patenting: Germany reconsidered

This paper provides new econometric evidence on the determinants of eco-innovations by using multiple innovation indicators and by combining survey-based information and patent records at the firm level from two different time periods. We hypothesize that firms with a propensity to patent focus on future technological and market opportunities and do not directly or immediately react to incentives created by environmental policies. Based on negative binomial models, we confirm that eco-patents are stimulated by the expectation of creating technological advancement and new market opportunities. By contrast, energy cost savings can better or more easily be achieved when firms refrain from patenting and concentrate on non-patented innovations or adoption. Favorable framework conditions created by environmental policies and patent protection are also important for eco-patenting, but more in the longer term. Testing the validity of using self-reported eco-innovations, instead of patents, as the dependent variable in simple binomial probit models reveals that product eco-innovations as reported in the surveys are a relatively good proxy for eco-patents. Yet, for product eco-innovations, serving and enlarging current markets is another important reason to innovate.     

Dynamic Calibration of an Acid Aerosol Analyzer

A method is described for dynamic calibration of an acid aerosol analyzer based on a commercial modification of the Thomas Autometer and manufactured by the Instrument Development Company. This automated instrument removes acid aerosol from an air stream by sonic impaction, and the sulfuric acid collected is determined conductometrically. An all-glass aerosol generator based on the reaction of water vapor with sulfur trioxide vapor released from fuming sulfuric acid was built for the calibration. Air samples were withdrawn for instrument calibration before and after the concentration of the acid aerosol was determined by titration. The apparent particle size as determined by an Andersen sampler ranged from 2.0 microns to less than 0.68 micron and exhibited a sharp peak with mass median diameter at 1.3 microns in the distribution curve. The size of the aerosol, within certain limits, could be controlled by humidity. Data indicated a linear response with an aerosol collection efficiency of 80 percent in the important respirable size range.     

Distribution of Light Hydrocarbons in Ambient Air

The diversity of hydrocarbons which are present in ambient polluted air provide a potentially rich source of information concerning the nature of this type of pollution. Measurements of the relative amounts of various hydrocarbons can be correlated with the various possible sources. Since hydrocarbon reactivities vary widely it is also possible to estimate the extent to which various individual hydrocarbons have reacted. Except for samples taken deliberately near sources of hydrocarbon pollution these air samples invariably resemble auto exhaust with an addition of natural gas and of C₃–C₅ paraffins which resemble gasoline vapor. Samples taken in industrial areas and near the smoke plume from a brush fire showed distinctive differences in composition. During the smog season in the fall of 1968 good data were obtained of “typical” or “representative” samples of light, medium and heavy smog. These show the expected depletion of more reactive hydrocarbons in a much more convincing way than before. By comparing these distributions with composition in unreacted samples and by making use of data from bottle irradiations, it was possible to estimate the contribution of the various hydrocarbons in terms of “amount reacted.” The amounts of higher hydrocarbons present and reacted were also estimated from gasoline composition.