Acid generation upon thermal concentration of natural water: The critical water content and the effects of ionic composition

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10–20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7–9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.     

Variability in environmental impacts of Brazilian soybean according to crop production and transport scenarios

Soybean production and its supply chain are highly dependent on inputs such as land, fertilizer, fuel, machines, pesticides and electricity. The expansion of this crop in Brazil in recent decades has generated concerns about its environmental impacts. To assess these impacts, two representative chains supplying soybeans to Europe were identified: Center West (CW) and Southern (SO) Brazil. Each supply chain was analyzed using Life Cycle Assessment methodology. We considered different levels of use of chemical and organic fertilizers, pesticides and machinery, different distances for transportation of inputs and different yield levels. Because transportation contributed strongly to environmental impacts, a detailed study was performed to identify the routes used to transport soybeans to seaports. Additionally, we considered different levels of land occupation and land transformation to represent the impact of deforestation in the CW region. Environmental impacts were calculated for 1000 kg of soybean up to and including the delivery to Europe at the seaport in Rotterdam, at 13% humidity. Overall results showed that the impacts are greater for CW than for SO for all impact categories studied, including acidification (7.7 and 5.3 kg SO₂ eq., respectively), climate change (959 and 510 kg CO₂ eq.), cumulative energy demand (12,634 and 6,999 MJ) and terrestrial ecotoxicity (4.9 and 3.1 kg 1,4-DCB eq.), except eutrophication and land occupation. The same trend was observed for the crop-production stage. Efforts to reduce chemical fertilizers and diesel consumption can reduce CO₂ emissions. Although deforestation for crop production has decreased in recent years, the contribution of deforestation to climate change and cumulative energy demand remains significant. In the CW scenario deforestation contributed 29% to climate change and 20% to cumulative energy demand. Results also showed that although there are different transportation options in Brazil, the current predominance of road transport causes severe environmental impacts. In CW, road transport contributed 19% to climate change and 24% to cumulative energy demand, while in SO it contributed 12% and 15% to these impacts, respectively. Improvements in the logistics of transportation, giving priority to rail and river transports over road transport, can contribute significantly to reducing greenhouse gas emissions and decreasing energy use. Future studies involving Brazilian soybeans should take into account the region of origin as different levels of environmental impact are predicted.     

Mixed-Grass Prairie Canopy Structure and Spectral Reflectance Vary with Topographic Position

Managers of the nearly 0.5 million ha of public lands in North and South Dakota, USA rely heavily on manual measurements of canopy height in autumn to ensure conservation of grassland structure for wildlife and forage for livestock. However, more comprehensive assessment of vegetation structure could be achieved for mixed-grass prairie by integrating field survey, topographic position (summit, mid and toeslope) and spectral reflectance data. Thus, we examined the variation of mixed-grass prairie structural attributes (canopy leaf area, standing crop mass, canopy height, nitrogen, and water content) and spectral vegetation indices (VIs) with variation in topographic position at the Grand River National Grassland (GRNG), South Dakota. We conducted the study on a 36,000-ha herbaceous area within the GRNG, where randomly selected plots (1?km² in size) were geolocated and included summit, mid and toeslope positions. We tested for effects of topographic position on measured vegetation attributes and VIs calculated from Landsat TM and Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data collected in July 2010. Leaf area, standing crop mass, canopy height, nitrogen, and water content were lower at summits than at toeslopes. The simple ratio of Landsat Band 7/Band 1 (SR71) was the VI most highly correlated with canopy standing crop and height at plot and landscape scales. Results suggest field and remote sensing-based grassland assessment techniques could more comprehensively target low structure areas at minimal expense by layering modeled imagery over a landscape stratified into topographic position groups.     

Modeling of Cs migration in soils using an 80-year soil archive: role of fertilizers and agricultural amendments

An 80-year soil archive, the 42-plot experimental design at the INRA in Versailles (France), is used here to study long-term contamination by ¹³⁷Cs atmospheric deposition and the fate of this radioisotope when associated with various agricultural practices: fallow land, KCl, NH₄(NO₃), superphosphate fertilizers, horse manure and lime amendments. The pertinence of a simple box model, where radiocaesium is supposed to move downward by convectional mechanisms, is checked using samples from control plots which had been neither amended, nor cultivated since 1928. This simple model presents the advantage of depending on only two parameters: α, a proportional factor allowing the historical atmospheric ¹³⁷Cs fluxes to be reconstructed locally, and k, an annual loss coefficient from the plow horizon. Another pseudo-unknown is however necessary to run the model: the shape of historical ¹³⁷Cs deposition, but this function can be easily computed by merging several curves previously established by other surveys. A loss of ∼1.5% per year from the plow horizon, combined with appropriate fluxes, provides good concordance between simulated and measured values. In the 0–25 cm horizon, the residence half time is found to be ∼18 yr (including both migration and radioactive decay). Migration rate constants are also calculated for some plots receiving continuous long-term agricultural treatments. Comparison with the control plots reveals significant influence of amendments on ¹³⁷Cs mobility in these soils developed from a unique genoform.     

δ 13C and δ 15N variations in organic matter pools, Mytilus spp. and Macoma balthica along the European Atlantic coast

Stable carbon (δ ¹³C) and nitrogen (δ ¹⁵N) isotope (SI) values of sedimentary organic matter (SOM), seston and two dominant bivalves, Mytilus spp. and Macoma balthica, were studied at 18 stations along the European coast in spring and autumn 2004. Three main regions, the Baltic Sea (BS), the North Sea and English Channel (NS), and the Bay of Biscay (BB), were tested for possible geographic (latitudinal) differences in the SI values. In spring, only BS showed lower δ ¹³C values of seston and Mytilus spp., and higher δ ¹⁵N values of SOM, than NS and BB. No significant differences between the 3 regions were found in autumn. Irrespective of season and regions, Mytilus spp. was more ¹³C-depleted than M. balthica. δ ¹³C values of M. balthica, but not those of Mytilus spp., were significantly correlated with SOM. These results are consistent with differences in feeding behavior of Mytilus spp. and M. balthica, as the two species are known as obligatory-suspension and facultative-deposit feeders, respectively. In contrast, no differences in the δ ¹⁵N values of Mytilus spp. and M. balthica were found at individual stations, indicating the same trophic level of the two bivalves within the food webs. At some stations, irrespective of geographic location, both bivalves showed δ ¹⁵N values up to 18–20 ‰. These were two trophic levels higher than those found at the other stations, indicating local and/or episodic eutrophic conditions, probably due to waste water discharge, and the effectiveness of both Mytilus spp. and M. balthica as bio-indicators of anthropogenic eutrophication. Overall, our results suggest that pathways of energy flow from OM pools to dominant bivalves is more related to local environmental conditions than to geographic regions across the European coastline. This has implications for food web studies along the Atlantic coast because most of the values are consistent over a large area and show no significant differences. Therefore, the present study can be used twofold for the determination of trophic baselines and for the correction of the trophic position of consumers higher up in the food web in the case of differences in waste water discharge.     

Spatial and seasonal variations in atrazine and metolachlor surface water concentrations in Ontario (Canada) using ELISA

Concerns regarding the impacts of pesticides on aquatic species and drinking water sources have increased demands on water quality monitoring programs; however the costs of sample analysis can be prohibitive. In this study we investigated enzyme-linked immunosorbent assay (ELISA) as a cost-effective, high through-put method for measuring pesticide concentrations in surface waters. Seven hundred and thirty-nine samples from 158 locations throughout Ontario were analysed for atrazine and metolachlor from April to October 2007. Concentrations ranged from <0.1 to 3.91 μg L⁻¹ (median = 0.12 μg L⁻¹) for atrazine and from <0.1 to 1.83 μg L⁻¹ (median = 0.09 μg L⁻¹) for metolachlor. Peak concentrations occurred in late spring/early summer, in rural agricultural locations, and decreased over the remainder of the growing season for both herbicides. About 3% of the samples that had ELISA results occurring above the limit of quantification (0.10 μg L⁻¹) were evaluated against gas chromatography-mass spectrometry (GC-MS). Linear regression analysis revealed a R² value of 0.88 and 0.39, for atrazine and metolachlor, respectively. ELISA tended to overestimate concentrations for atrazine and metolachlor, most likely because the ELISA kits also detect their metabolites. Atrazine data suggest that ELISA may be used complementary with GC-MS analysis to enhance the spatial and temporal resolution of a water quality monitoring study. The commercially available metolachlor ELISA kit requires further investigation. ELISA may be used to detect atrazine and metolachlor in surface water samples, but it is not recommended as a quantitative replacement for traditional analytical methods.     

Toxicity of zinc oxide nanoparticles in the earthworm, Eisenia fetida and subcellular fractionation of Zn

The extensive use of nanoparticles (NPs) in a variety of applications has raised great concerns about their environmental fate and biological effects. This study examined the impact of dissolved organic matter (DOM) and salts on ZnO NP dispersion/solubility and toxicity to the earthworm Eisenia fetida. To be able to better evaluate the toxicity of NPs, exposure in agar and on filter paper was proposed for enabling a comparison of the importance of different uptake routes. A dose-related increase in mortality was observed in earthworms exposed in agar with almost 100% mortality after 96 h exposure to the highest concentration (1000 mg ZnO/kg agar). Scanning electron microscopy (SEM) showed that the addition of salts enhanced the aggregation of ZnO NPs in agar and consequently affected the dissolution behavior and biological availability of the particles. On filter paper, mortality was the highest at the lowest exposure concentration (50 mg ZnO/L) and seemed to decrease with increasing exposure levels. TEM images of ZnO showed that the solubility and morphology of NPs were changed dramatically upon the addition of humic acids (HA). The subcellular distribution pattern of Zn in earthworms after 96 h exposure in agar and on filter paper showed that the Zn taken up via dietary ZnO particles (from agar) was mainly found in organelles and the cytosol while the Zn accumulated as soluble Zn from filter paper was mainly distributed in cell membranes and tissues. Antioxidant enzymatic activities (SOD, CAT, and GSH-px) were investigated in the worms surviving the toxicity tests. A slight increase of SOD activities was observed at the lowest exposure dose of ZnO (50mg/kg), followed by a decrease at 100mg/kg in the agar cubes. Activities of both CAT and GSH-Px enzymes were not significantly influenced in the worms exposed to agar, although a slight decrease at 500 and 1000 mg ZnO/kg agar was observed. A similar change trend of SOD activities was observed for the earthworms on filter paper, but a significant decrease began at a higher ZnO NP concentration of 500 mg ZnO/L. The use of soil extracts instead of deionized water (DW) to simulate a realistic exposure system significantly reduced the toxicity of the ZnO NPs on filter paper, which increases the predictive power of filter paper toxicity tests for the environmental risk assessment of NPs.     

The contemporary cement cycle of the United States

A country-level stock and flow model for cement, an important construction material, was developed based on a material flow analysis framework. Using this model, the contemporary cement cycle of the United States was constructed by analyzing production, import, and export data for different stages of the cement cycle. The United States currently supplies approximately 80% of its cement consumption through domestic production and the rest is imported. The average annual net addition of in-use new cement stock over the period 2000–2004 was approximately 83 million metric tons and amounts to 2.3 tons per capita of concrete. Nonfuel carbon dioxide emissions (42 million metric tons per year) from the calcination phase of cement manufacture account for 62% of the total 68 million tons per year of cement production residues. The end-of-life cement discards are estimated to be 33 million metric tons per year, of which between 30% and 80% is recycled. A significant portion of the infrastructure in the United States is reaching the end of its useful life and will need to be replaced or rehabilitated; this could require far more cement than might be expected from economic forecasts of demand for cement.