Use of the Critical Acidification Model to Estimate the Influence of W in the Localized Corrosion Resistance of 25Cr Super Duplex Stainless Steels

Two super duplex stainless steels (SDSS) with different W content, namely UNS S32750 (W-free) and UNS S39274 (2.1 wt.% W), were tested in simulated crevice corrosion environments to determine the influence of W on their corrosion resistance. Anodic potentiodynamic polarization experiments were performed in two different crevice-like-solutions: 1 M HCl (as reference for a pH = 0 environment), and 7 M LiCl, adjusted to the same pH value. Galvele’s critical acidification model was used to estimate the theoretical critical potential (Ecrit) and comparatively evaluate the corrosion resistance of the two SDSS. The anodic potentiodynamic polarization results showed a statistically significant difference between the two materials in only one test condition, i.e., 7 M Cl− at 60 °C. Additionally, the quantification of chemical dissolution of the metal cations after the tests suggested a surface enrichment in W only in the 7 M chloride solution. Scanning electron microscope (SEM) analysis indicated a uniform dissolution experienced by UNS S32750 in this environment, whereas UNS S39274 suffered selective corrosion of the ferrite-phase. These observations were reflected in a slight increase in the Ecrit values of UNS S32974 estimated with Galvele’s model.

Modelling the recovery of acid-sensitive Finnish headwater lakes under present emission reduction agreements

Abstract: Over the past two decades, substantial reductions in the deposition of acidifying substances (primarily sulphur) have occurred in most parts of Europe and, following recent agreements, this trend is likely to continue. The question arises as to how have sensitive ecosystems reacted, and will react in the future, to these reduced inputs of acidity? In this paper, the SMART dynamic acidification model predicts the possible recovery of 36 acid-sensitive Finnish headwater lakes, for which both catchment soil and water quality measurements were available. The model was calibrated to measurements by adjusting poorly known parameters; it was then used to simulate soil and water chemistry until 2030 under the ‘current legislation scenario’ resulting from implementing current European emission reduction agreements. Whereas most of the catchment soils show very little change in base saturation, the positive trends in lake ANC and the negative trends in lake sulphate concentrations, observed over the past decade, continue into the future, albeit at a slower pace. The model predicts that, during 2010–30, all lakes will have reached a positive ANC, a pre-requisite for the recovery of fish populations. Keywords: acidification, lake, catchment, recovery, SMART model, Finland

Modelling the response of soil and soil solution chemistry upon roofing a forest in an area with high nitrogen deposition

In the Speuld forest, the Netherlands, the dynamic soil acidification model NuCSAM has been applied to a manipulation experiment in which part of the forest was roofed to control nitrogen (N) and sulphur (S) deposition. The roofed area was divided into two subplots watered artificially; one received ambient N and S deposition and one with pristine N and S deposition. Concentration measurements on each plots showed a high (time-dependent) spatial variability. Statistical analyses of the concentrations on both subplots showed small but significant effects of the reduction in deposition on nitrate (NO3) sulphate (SO4) and aluminum (Al) concentrations. The statistical significance of the effects was minimised by the large spatial variability within the plots. Despite these shortcomings, simulated concentrations were generally within the 95% confidence interval of the measurements although the effect of a reduction in N deposition on soil solution chemistry was underestimated due to a marked decline in N-uptake by the vegetation.

Comparison of simulated forest soil response to acid deposition reduction with two models of differing complexity

Great effort has been dedicated to developing soil acidification models for use on different scales. This paper focuses on the changes in model performance of a site scale soil acidification model (NUCSAM) and a national to European scale soil acidification model (SMART 2). This was done to gain insight into the effects of model simplification. Because these models aim to predict the response to reduction in acid deposition, these models must be tested under such circumstances. A straightforward calibration and validation of the regional model, however, is hampered by lack of observations over a sufficient time period. Consequently, NUCSAM was calibrated and validated to a manipulation experiment involving reduced acid deposition in the Speuld forest, the Netherlands. SMART 2 was then used with calibrated input data from NUCSAM. The acid deposition was excluded by a roof beneath the canopy. The roofed area consists of a plot receiving pristine deposition levels of nitrogen (N) and sulphur (S) and a control plot receiving ambient deposition. NUCSAM was calibrated on the ambient plot, followed by a validation of both models on the pristine plot. Both models predicted soil solution concentrations within the 95% confidence interval of the observed responses for both the ambient plot and the pristine plot at 90 cm depth. Despite the large seasonal and vertical (spatial) variation in soil solution chemistry, the trends in annual flux- weighted soil solution chemistry, as predicted by SMART 2 and NUCSAM, corresponded well.The annual leaching fluxes below the root zone were also similar although differences exist for the topsoil. For the topsoil, NUCSAM simulated the nutrients and acid related constituents better than SMART 2. Both models overestimated the ammonium (NH4) concentration at 10 cm depth. SMART 2 underestimated calcium and magnesium (BC2+) concentration at 10 depth, whereas NUCSAM overestimated BC2+ concentration at 90 cm depth. NUCSAM predicted the effect of deposition reduction on N concentrations at both depths, whereas SMART 2 underestimated the effect of deposition reduction at 10 cm depth. Both models predicted faster effects of deposition reduction on aluminum (Al), sulphate (SO4) and base cations than was observed. Generally, it appeared that the differences were large during the period of profound deposition changes whereas small differences occurred during slight variations in deposition level. It is concluded that a simpler model description does not affect the model's performance significantly as regards flux-weighted annual average concentrations at greater depth. Model improvements must focus on processes related to N-dynamics.