Precipitation studies on alloys from the system copper chromium zirconium

The precipitation reactions occurring in a series of copper-based alloys selected from the system copper-chromium-zirconium have been studied by resistometric and metallographic techniques. A survey of the factors influencing the development of copper-based alloys for high strength, high conductivity applications is followed by a more general review of contemporary materials, and illustrates that the most promising alloys are those containing chromium and zirconium. The few systematic attempts to study alloys from this system have been collated, discussed, and used as a basis for the selection of four alloy compositions viz:- Cu - 0.4% Cr Cu - 0.24. Zr Cu - 0. 3% Cr - 0.1% Zr Cu - 0.2% Cr - 0.2% Zr A description of the experimental techniques used to study the precipitation behaviour of these materials is preceeded by a discussion of the currently accepted theories relating to precipitate nucleation and growth. The experimental results are presented and discussed for each of the alloys independently, and are then treated jointly to obtain an overall assessment of the way in which the precipitation kinetics, metallography and mechanical properties vary with alloy composition and heat treatment. The metastable solid solution of copper-chromium is found to decompose by the rejection of chromium particles which maintain a coherent interface and a Kurdjumov-Sachs type crystallographic orientation relationship with the copper matrix. The addition of 0.1% zirconium to the alloy retards the rate of transformation by a factor of ten and modifies the dispersion characteristics of the precipitate without markedly altering the morphology. Further additions of zirconium lead to the growth of stacking faults during ageing, which provide favourable nucleation sites for the chromium precipitate. The partial dislocations bounding such stacking faults are also found to provide mobile heterogeneous nucleation sources for the precipitation reactions occurring in copper-zirconium.

Estimate of the (R)USLE rainfall erosivity factor from monthly precipitation data in mainland Spain

The need for continuous recording rain gauges makes it difficult to determine the rainfall erosivity factor (R-factor) of the (R)USLE model in areas without good temporal data coverage. In mainland Spain, the Nature Conservation Institute (ICONA) determined the R-factor at few selected pluviographs, so simple estimates of the R-factor are definitely of great interest. The objectives of this study were: (1) to identify a readily available estimate of the R-factor for mainland Spain; (2) to discuss the applicability of a single (global) estimate based on analysis of regional results; (3) to evaluate the effect of record length on estimate precision and accuracy; and (4) to validate an available regression model developed by ICONA. Four estimators based on monthly precipitation were computed at 74 rainfall stations throughout mainland Spain. The regression analysis conducted at a global level clearly showed that modified Fournier index (MFI) ranked first among all assessed indexes. Applicability of this preliminary global model across mainland Spain was evaluated by analyzing regression results obtained at a regional level. It was found that three contiguous regions of eastern Spain (Catalonia, Valencian Community and Murcia) could have a different rainfall erosivity pattern, so a new regression analysis was conducted by dividing mainland Spain into two areas: Eastern Spain and plateau-lowland area. A comparative analysis concluded that the bi-areal regression model based on MFI for a 10-year record length provided a simple, precise and accurate estimate of the R-factor in mainland Spain. Finally, validation of the regression model proposed by ICONA showed that R-ICONA index overpredicted the R-factor by approximately 19%.

Environmental impacts of freshwater use and suspended solids in life cycle assessment

Perturbation of natural ecosystems, namely by increasing freshwater use and its degradative use, as well as topsoil erosion by water of land-use production systems, have been emerging as topics of high environmental concern. Freshwater use has become a focus of attention in the last few years for all stakeholders involved in the production of goods, mainly agro-industrial and forest-based products, which are freshwater-intensive consumers, requiring large inputs of green and blue water. This thesis presents a global review on the available Water Footprint Assessment and Life Cycle Assessment (LCA)-based methods for measuring and assessing the environmental relevance of freshwater resources use, based on a life cycle perspective. Using some of the available midpoint LCA-based methods, the freshwater use-related impacts of a Portuguese wine (white ‘vinho verde’) were assessed. However, the relevance of environmental green water has been neglected because of the absence of a comprehensive impact assessment method associated with green water flows. To overcome this constraint, this thesis helps to improve and enhance the LCA-based methods by providing a midpoint and spatially explicit Life Cycle Impact Assessment (LCIA) method for assessing impacts on terrestrial green water flow and addressing reductions in surface blue water production caused by reductions in surface runoff due to land-use production systems. The applicability of the proposed method is illustrated by a case study on Eucalyptus globulus conducted in Portugal, as the growth of short rotation forestry is largely dependent on local precipitation. Topsoil erosion by water has been characterised as one of the most upsetting problems for rivers. Because of this, this thesis also focuses on the ecosystem impacts caused by suspended solids (SS) from topsoil erosion that reach freshwater systems. A framework to conduct a spatially distributed SS delivery to freshwater streams and a fate and effect LCIA method to derive site-specific characterisation factors (CFs) for endpoint damage on aquatic ecosystem diversity, namely on algae, macrophyte, and macroinvertebrates organisms, were developed. The applicability of this framework, combined with the derived site-specific CFs, is shown by conducting a case study on E. globulus stands located in Portugal as an example of a land use based system. A spatially explicit LCA assessment was shown to be necessary, since the impacts associated with both green water flows and SS vary greatly as a function of spatial location.

A comparison of in situ vs. ex situ filtration methods on the assessment of dissolved and particulate metals at hydrothermal vents

The objective of this study was to assess the impact of the filtration method (in situ vs. ex situ) on the dissolved/particulate partitioning of 12 elements in hydrothermal samples collected from the Lucky Strike vent field (Mid-Atlantic Ridge; MAR). To do so, dissolved ( <0.45 mu m) and particulate Mg, Li, Mn, U, V, As, Ba, Fe, Zn, Cd, Pb and Cu were measured using different techniques (HR-ICP-MS, ICP-AES and CCSA). Using in situ filtration as a baseline, we showed that ex situ filtration (on-board and on shore after freezing) resulted in an underestimation of the dissolved pool, which was counterbalanced by an overestimation of the particulate pool for almost all the elements studied. We also showed that on-board filtration was acceptable for the assessment of dissolved and particulate Mn, Mg, Li and U for which the measurement bias for the dissolved fraction did not exceed 3%. However, in situ filtration appeared necessary for the accurate assessment of the dissolved and particulate concentrations of V, As, Fe, Zn, Ba, Cd, Pb and Cu. In the case of Fe, on-board filtration underestimated the dissolved pool by up to 96%. Laboratory filtration (after freezing) resulted in a large bias in the dissolved and particulate concentrations, unambiguously discounting this filtration method for deep-sea chemical speciation studies. We discuss our results in light of the precipitation processes that can potentially affect the accuracy of ex situ filtration methods.

Environmental assessment of proton exchange membrane fuel cell platinum catalyst recycling

International audience

Modeling Flood Stage-Duration-Frequency: A Risk Assessment of Critical Infrastructure in the Tidal Potomac

The service of a critical infrastructure, such as a municipal wastewater treatment plant (MWWTP), is taken for granted until a flood or another low frequency, high consequence crisis brings its fragility to attention. The unique aspects of the MWWTP call for a method to quantify the flood stage-duration-frequency relationship. By developing a bivariate joint distribution model of flood stage and duration, this study adds a second dimension, time, into flood risk studies. A new parameter, inter-event time, is developed to further illustrate the effect of event separation on the frequency assessment. The method is tested on riverine, estuary and tidal sites in the Mid-Atlantic region. Equipment damage functions are characterized by linear and step damage models. The Expected Annual Damage (EAD) of the underground equipment is further estimated by the parametric joint distribution model, which is a function of both flood stage and duration, demonstrating the application of the bivariate model in risk assessment. Flood likelihood may alter due to climate change. A sensitivity analysis method is developed to assess future flood risk by estimating flood frequency under conditions of higher sea level and stream flow response to increased precipitation intensity. Scenarios based on steady and unsteady flow analysis are generated for current climate, future climate within this century, and future climate beyond this century, consistent with the WWTP planning horizons. The spatial extent of flood risk is visualized by inundation mapping and GIS-Assisted Risk Register (GARR). This research will help the stakeholders of the critical infrastructure be aware of the flood risk, vulnerability, and the inherent uncertainty.

Sediment toxicity assessment of Guanabara Bay, Rio de Janeiro, Brazil.

Guanabara Bay (GB) comprises of estuarine and marine environments of high ecological and socio-economic relevance, together with port, industrial and urban areas. The anthropogenic activities produce environmental impacts, including the aquatic pollution. The sediment quality assessment is important to evaluate the effects of contamination, once sediments are a repository for most of the contaminants. In this Study, the quality of sediments from GB was evaluated, in rainy and dry periods, throughout the employment of acute toxicity tests with the amphipod Tiburonella viscana, and chronic bioassays with embryos of the sea-urchin Lytechinus variegatus. In the dry period, acute toxicity was found in the sediments from stations 1, 2 3 (NW) and 7 (near Guapimirim Environmental Protection Area). The bioassays with liquid phases showed effects, but were strongly influenced by the unionized ammonia levels, which were high in this period. In the rainy period, acute toxicity was found in sediments samples from stations 1, 2, 3, 6, 8, 10, 11, 12 and 15. Chronic toxicity could be clearly detected, as ammonia concentrations tended to be low in the most part of the samples. The results showed that the sediment toxicity is influenced by precipitation rates, which increase the input of contaminants to the Bay, and also allowed subdividing GB in three main zones: northwest (stations 1, 2, 3, 5), northeast (stations 6, 7, 8, 9) and centre-south (stations 10, 11, 12, 13, 14, 15). Results also showed that the quality of GB sediments is poor, and that toxicity tests could determine the combined effects of pollutants.

Assessment of molecular sequences and enzyme activity of amylase trypsin inhibitors (ATIs) from a selection of ancient and modern grains

Wheat amylase-trypsin inhibitors (ATIs) are a family of wheat proteins, which play an important role in plant defence against pest attacks. ATIs are also of great interest for their impact on human health and recently ATIs have been identified as major stimulators of innate immune cells. In this study, ten selected wheat samples with different ploidy level and year of release were used for the agronomic trial, for in vitro enzymatic assays and for ATIs gene sequencing. Wheat samples were grown under organic farming management during three consecutive cropping years at two growing areas (Italy and USA). The PCA analysis performed on the deduced amino acid sequences of four representative ATIs genes (WMAI, WDAI, WTAI-CM3, CMx) evidenced that the ten wheat varieties can be differentiated on the basis of their ploidy level, but not with respect to ancient or recently developed wheat genotypes. The results from in vitro alpha-amylase and trypsin inhibitory activities showed high variability among the ten wheat genotypes and the contribution of the genotype and the cropping year was significant for both inhibitory activities. The hexaploid wheat genotypes showed the highest inhibitory activities. Einkorn showed a very low or even absent alpha-amylase inhibitory activity and the highest trypsin inhibitory activity. It was not possible to differentiate ancient and recently developed wheat genotypes on the basis of their ATIs activity. The weather conditions differently affected the two inhibitory activities. In both cultivation areas, higher precipitation and lower high mean temperatures correlated with lower alpha-amylase inhibitory activities, while there were different correlations considering trypsin inhibitory activity for the two growing areas. The protein content negatively correlated with both inhibitory activities in USA and Italy. This information can be important in the understanding of plant defence mechanisms in relation to the effect of both genotype and abiotic and biotic stress.

Comprehensive characterization of snowfall in terms of microphysical features, quantitative precipitation estimation and scavenging properties by in situ and remote sensing observations at an Antarctic coastal site

Snow plays a crucial role in the Earth's hydrological cycle and energy budget, making its monitoring necessary. In this context, ground-based radars and in situ instruments are essential thanks to their spatial coverage, resolution, and temporal sampling. Deep understanding and reliable measurements of snow properties are crucial over Antarctica to assess potential future changes of the surface mass balance (SMB) and define the contribution of the Antarctic ice sheet on sea-level rise. However, despite its key role, Antarctic precipitation is poorly investigated due to the continent's inaccessibility and extreme environment. In this framework, this Thesis aims to contribute to filling this gap by in-depth characterization of Antarctic precipitation at the Mario Zucchelli station from different points of view: microphysical features, quantitative precipitation estimation (QPE), vertical structure of precipitation, and scavenging properties. For this purpose, a K-band vertically pointing radar collocated with a laser disdrometer and an optical particle counter (OPC) were used. The radar probed the lowest atmospheric layers with high vertical resolution, allowing the first trusted measurement at only 105 m height. Disdrometer and OPC provided information on the particle size distribution and aerosol concentrations. An innovative snow classification methodology was designed by comparing the radar reflectivity (Ze) and disdrometer-derived reflectivity by means of DDA simulations. Results of classification were exploited in QPE through appropriate Ze-snow rate relationships. The accuracy of the resulting QPE was benchmarked against a collocated weighing gauge. Vertical radar profiles were also investigated to highlight hydrometeors' sublimation and growth processes. Finally, OPC and disdrometer data allowed providing the first-ever estimates of scavenging properties of Antarctic snowfall. Results presented in this Thesis give rise to advances in knowledge of the characteristics of snowfall in Antarctica, contributing to a better assessment of the SMB of the Antarctic ice sheet, the major player in the global sea-level rise.

Assessment Of The Fixation Of Mandibular Symphysis Fractures Using Conical Cannulated Screws: Mechanical And Photoelastic Tests.

The aim of this study was to use mechanical and photoelastic tests to compare the performance of cannulated screws with other fixation methods in mandibular symphysis fractures. Ten polyurethane mandibles were allocated to each group and fixed as follows: group PRP, 2 perpendicular miniplates; group PLL, 1 miniplate and 1 plate, parallel; and group CS, 2 cannulated screws. Vertical linear loading tests were performed. The differences between mean values were analyzed with the Tukey test. The photoelastic test was carried out using a polariscope. The results revealed differences between the CS and PRP groups at 1, 3, 5, and 10 millimeters of displacement. The photoelastic test confirmed higher stress concentration in all groups close to the mandibular base, whereas the CS group showed it throughout the region assessed. Conical cannulated screws performed well in mechanical and photoelastic tests.

Cardiac Magnetic Resonance Assessment Of Interstitial Myocardial Fibrosis And Cardiomyocyte Hypertrophy In Hypertensive Mice Treated With Spironolactone.

Nearly 50% of patients with heart failure (HF) have preserved LV ejection fraction, with interstitial fibrosis and cardiomyocyte hypertrophy as early manifestations of pressure overload. However, methods to assess both tissue characteristics dynamically and noninvasively with therapy are lacking. We measured the effects of mineralocorticoid receptor blockade on tissue phenotypes in LV pressure overload using cardiac magnetic resonance (CMR). Mice were randomized to l-nitro-ω-methyl ester (l-NAME, 3 mg/mL in water; n=22), or l-NAME with spironolactone (50 mg/kg/day in subcutaneous pellets; n=21). Myocardial extracellular volume (ECV; marker of diffuse interstitial fibrosis) and the intracellular lifetime of water (τic; marker of cardiomyocyte hypertrophy) were determined by CMR T1 imaging at baseline and after 7 weeks of therapy alongside histological assessments. Administration of l-NAME induced hypertensive heart disease in mice, with increases in mean arterial pressure, LV mass, ECV, and τic compared with placebo-treated controls, while LV ejection fraction was preserved (>50%). In comparison, animals receiving both spironolactone and l-NAME (l-NAME+S) showed less concentric remodeling, and a lower myocardial ECV and τic, indicating decreased interstitial fibrosis and cardiomyocyte hypertrophy (ECV: 0.43 ± 0.09 for l-NAME versus 0.25 ± 0.03 for l-NAME+S, P<0.001; τic: 0.42 ± 0.11 for l-NAME groups versus 0.12 ± 0.05 for l-NAME+S group). Mice treated with a combination of l-NAME and spironolactone were similar to placebo-treated controls at 7 weeks. Spironolactone attenuates interstitial fibrosis and cardiomyocyte hypertrophy in hypertensive heart disease. CMR can phenotype myocardial tissue remodeling in pressure-overload, furthering our understanding of HF progression.

The Inadequacy Of The Y-axis Of Growth (sngn) For The Vertical Pattern Assessment In Patients With Sagittal Discrepancies.

The aim of this cephalometric study was to evaluate the influence of the sagittal skeletal pattern on the 'Y-axis of growth' measurement in patients with different malocclusions. Lateral head films from 59 patients (mean age 16y 7m, ranging from 11 to 25 years) were selected after a subjective analysis of 1630 cases. Sample was grouped as follows: Group 1 - class I facial pattern; group 2 - class II facial pattern; and Group 3 - class III facial pattern. Two angular measurements, SNGoGn and SNGn, were taken in order to determine skeletal vertical facial pattern. A logistic regression with errors distributed according to a binomial distribution was used to test the influence of the sagittal relationship (Class I, II, III facial patterns) on vertical diagnostic measurement congruence (SNGoGn and SNGn). RESULTS show that the probability of congruence between the patterns SNGn and SNGoGn was relatively high (70%) for group 1, but for groups II (46%) and III (37%) this congruence was relatively low. The use of SNGn appears to be inappropriate to determine the vertical facial skeletal pattern of patients, due to Gn point shifting throughout sagittal discrepancies. Clinical Significance: Facial pattern determined by SNGn must be considered carefully, especially when severe sagittal discrepancies are present.

Assessment Of Robustness On Analysis Using Headspace Solid-phase Microextraction And Comprehensive Two-dimensional Gas Chromatography Through Experimental Designs.

Plackett-Burman experimental design was applied for the robustness assessment of GC×GC-qMS (Comprehensive Two-Dimensional Gas Chromatography with Fast Quadrupolar Mass Spectrometric Detection) in quantitative and qualitative analysis of volatiles compounds from chocolate samples isolated by headspace solid-phase microextraction (HS-SPME). The influence of small changes around the nominal level of six factors deemed as important on peak areas (carrier gas flow rate, modulation period, temperature of ionic source, MS photomultiplier power, injector temperature and interface temperature) and of four factors considered as potentially influential on spectral quality (minimum and maximum limits of the scanned mass ranges, ions source temperature and photomultiplier power). The analytes selected for the study were 2,3,5-trimethylpyrazine, 2-octanone, octanal, 2-pentyl-furan, 2,3,5,6-tetramethylpyrazine, and 2-nonanone e nonanal. The factors pointed out as important on the robustness of the system were photomultiplier power for quantitative analysis and lower limit of mass scanning range for qualitative analysis.

Bacterial Diversity Assessment In Soil Of An Active Brazilian Copper Mine Using High-throughput Sequencing Of 16s Rdna Amplicons.

Mining activities pose severe environmental risks worldwide, generating extreme pH conditions and high concentrations of heavy metals, which can have major impacts on the survival of organisms. In this work, pyrosequencing of the V3 region of the 16S rDNA was used to analyze the bacterial communities in soil samples from a Brazilian copper mine. For the analysis, soil samples were collected from the slopes (geotechnical structures) and the surrounding drainage of the Sossego mine (comprising the Sossego and Sequeirinho deposits). The results revealed complex bacterial diversity, and there was no influence of deposit geographic location on the composition of the communities. However, the environment type played an important role in bacterial community divergence; the composition and frequency of OTUs in the slope samples were different from those of the surrounding drainage samples, and Acidobacteria, Chloroflexi, Firmicutes, and Gammaproteobacteria were responsible for the observed difference. Chemical analysis indicated that both types of sample presented a high metal content, while the amounts of organic matter and water were higher in the surrounding drainage samples. Non-metric multidimensional scaling (N-MDS) analysis identified organic matter and water as important distinguishing factors between the bacterial communities from the two types of mine environment. Although habitat-specific OTUs were found in both environments, they were more abundant in the surrounding drainage samples (around 50 %), and contributed to the higher bacterial diversity found in this habitat. The slope samples were dominated by a smaller number of phyla, especially Firmicutes. The bacterial communities from the slope and surrounding drainage samples were different in structure and composition, and the organic matter and water present in these environments contributed to the observed differences.

[the Modified Us7 Score In The Assessment Of Synovitis In Early Rheumatoid Arthritis].

To evaluate the modified US7 score (MUS7 score SYN) in the assessment of patients with early rheumatoid arthritis (ERA). In addition, dorsal and palmar recesses of the wrists as well as of small joints of the hands and feet were examined for the presence of synovitis by means of a global assessment of joints. The study sample comprised 32 patients treated for arthritis, with an average disease duration of 13 months. An ultrasound machine with high frequency transducer was used. Hands were also X-rayed and analysed by Larsen score. Out of the 832 examined joints, synovitis was detected in 173 (20,79%), tenosynovitis in 22 (4,91%), and erosions in 3 (1,56%). Synovitis was predominantly detected in the dorsal recess (73,38%) of MCP and PIP joints, when compared with palmar recess (26%). The presence of synovitis in the joints evaluated correlated with clinical (HAQ-DI, DAS28), laboratory (ACPA, RF, CRP), and ultrasound results (r = 0,37 to r = 0,42; p = 0,04 to p = 0,003). We found correlation of the MUS7 score SYN of the gray scale US or of the power Doppler US with DAS28 (PCR) values (r = 0,38; p = 0,0332), and with CRP results (r = 0,39; p = 0,0280), respectively. The dorsal recess, the wrist, and small joints can be considered as important sites to detect synovitis by the MUS7 score SYN in patients with ERA.