Corrosion of stainless steel components in seawater reverse osmosis desalination plants-investigations on adapted internal cathodic protection

Stainless steel is widely used in seawater reverse osmosis units (SWRO) for both good mechanical and corrosion resistance properties. However, many corrosion failures of stainless steel in SWRO desalination units have been reported. These failures may often be attributed to un-adapted stainless steel grade selection and/or to the particular aggressive seawater conditions in "warm" regions (high ambient temperature, severe biofouling, etc.). Cathodic protection (CP) is a well-known efficient system to prevent corrosion of metallic materials in seawater. It is successfully used in the oil and gas industry to protect carbon steel structures exposed in open-sea. However, the specific service conditions of SWRO units may seriously affect the efficiency of such anti-corrosion system (high flow rates, large stainless steel surfaces affected by biofouling, confinement limiting protective cathodic current flow, etc.). Hence, CP in SWRO units should be considered with special care and modeling appears as useful tool to assess an appropriate CP design. However, there is a clear lack of CP data that could be transposed to SWRO service conditions (i.e. stainless steel, effect of biofouling, high flow rate, etc.). From this background a Join Industry Program was initiated including laboratory exposures, field measurements in a full scale SWRO desalination plant, and modeling work using PROCOR software. The present paper reviews the main parameters affecting corrosion of stainless steel alloys in seawater reverse osmosis units. CP on specific stainless steel devices was investigated in order to assess its actual efficiency for SWRO units. Severe environmental conditions were intentionally used to promote corrosion on the tested stainless steel products in order to evaluate the efficiency of CP. The study includes a modeling work aiming at predicting and designing adapted CP protection to modeled stainless steel units. An excellent correlation between modeling work and field measurements was found.

Water Stress Reveals Differential Antioxidant Responses Of Tolerant And Non-tolerant Sugarcane Genotypes.

The biochemical responses of the enzymatic antioxidant system of a drought-tolerant cultivar (IACSP 94-2094) and a commercial cultivar in Brazil (IACSP 95-5000) grown under two levels of soil water restriction (70% and 30% Soil Available Water Content) were investigated. IACSP 94-2094 exhibited one additional active superoxide dismutase (Cu/Zn-SOD VI) isoenzyme in comparison to IACSP 95-5000, possibly contributing to the heightened response of IACSP 94-2094 to the induced stress. The total glutathione reductase (GR) activity increased substantially in IACSP 94-2094 under conditions of severe water stress; however, the appearance of a new GR isoenzyme and the disappearance of another isoenzyme were found not to be related to the stress response because the cultivars from both treatment groups (control and water restrictions) exhibited identical changes. Catalase (CAT) activity seems to have a more direct role in H2O2 detoxification under water stress condition and the shift in isoenzymes in the tolerant cultivar might have contributed to this response, which may be dependent upon the location where the excessive H2O2 is being produced under stress. The improved performance of IACSP 94-2094 under drought stress was associated with a more efficient antioxidant system response, particularly under conditions of mild stress.

Physiological limitations in two sugarcane varieties under water suppression and after recovering

Increasing water scarcity and depleted water productivity in irrigated soils are inducing farmers to adopt improved varieties, such as those with high-capacity tolerance. The use of tolerant varieties of sugarcane might substantially avoid the decline of productivity under water deficit. This research aimed to evaluate the harmful effects of drought on the physiology of two sugarcane varieties (RB867515 and RB962962) during the initial development. Young plants were subjected to irrigation suspension until total stomata closure, and then rewatered. Significant reduction on stomatal conductance, transpiration, and net photosynthesis were observed. RB867515 showed a faster stomatal closure while RB962962 slowed the effects of drought on the gas exchanges parameters with a faster recovering after rewatering. Accumulation of carbohydrates, amino acids, proline, and protein in the leaves and roots of the stressed plants occurred in both varieties, substantially linked to reduction of the leaf water potential. Due to the severity of stress, this accumulation was not enough to maintain the cell turgor pressure, so relative water content was diminished. Water stress affected the contents of chlorophyll (a, b, and total) in both varieties, but not the levels of carotenoids. There was a significant reduction in dry matter under stress. In conclusion, RB962962 variety endured stressed conditions more than RB867515, since it slowed down the damaging effects of drought on the gas exchanges. In addition, RB962962 presented a faster recovery than RB867515, a feature that qualifies it as a variety capable of enduring short periods of drought without major losses in the initial stage of its development.

Analyzing the n→π* Electronic Transition of Formaldehyde in Water. A Sequential Monte Carlo/Time-Dependent Density Functional Theory

The n→π* absorption transition of formaldehyde in water is analyzed using combined and sequential classical Monte Carlo (MC) simulations and quantum mechanics (QM) calculations. MC simulations generate the liquid solute-solvent structures for subsequent QM calculations. Using time-dependent density functional theory in a localized set of gaussian basis functions (TD-DFT/6-311++G(d,p)) calculations are made on statistically relevant configurations to obtain the average solvatochromic shift. All results presented here use the electrostatic embedding of the solvent. The statistically converged average result obtained of 2300 cm-1 is compared to previous theoretical results available. Analysis is made of the effective dipole moment of the hydrogen-bonded shell and how it could be held responsible for the polarization of the solvent molecules in the outer solvation shells.

Gas-phase solvolysis type reactions of SiCl3+ cations

Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.

Solid-phase microextraction for determination of 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone in water

Solid-phase microextraction, using on-line bis(trimethylsilyl)trifluoroacetamide derivatisation, gas chromatography, and mass spectrometry, was evaluated in the quantification of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) in water samples. Fibres encompassing a wide range of polarities were used with headspace and direct immersion sampling. For the immersion procedure, various parameters affecting MX extraction, including pH, salinity, temperature, and extraction time were evaluated. The optimised method (polyacrylate fibre; 20% Na2SO4; pH 2.0; 60 min; 20 °C) was applied for reservoir chlorinated water samples-either natural or spiked with MX (50 ng L-1 and 100 ng L-1). The recovery of MX ranged from 44 to 72%. Quantification of MX in water samples was done using external standard and the selected ion monitoring mode. Correlation coefficient (0.98%), relative standard deviation (5%), limit of detection (30 ng L-1) and limit of quantification (50 ng L-1) were obtained from calibration curve.

Eucalyptus sp seedling response to potassium fertilization and soil water

A considerable portion of Brazil's commercial eucalypt plantations is located in areas Subjected to periods of water deficit and grown in soils with low natural fertility, particularly poor In potassium. Potassium is influential in controlling water relations of plants. The objective of this study was to verify the influence of potassium fertilization and soil water potential (psi(w)) oil the dry matter production and oil water relations Of eucalypt seedlings grown under greenhouse conditions. the experimental units were arranged in 4x4x2 randomized blocks factorial design, as follow: four species of Eucalyptus (Eucalyptus grandis, Eucalyptus urophylla, Eucalyptus camaldulensis and hybrid Eucalyptus grandis x Eucalyptus urophylla), four dosages of K (0, 50, 100 and 200 mg dm(-3)) and two soil water potentials (-0.01 M Pa and -0.1 M Pa). Plastic containers with 15 cm diameter and 18 cm height, with Styrofoam base, containing 3.0 dm(3) of soil and two plants per container were used. Soil water potential was kept at -0.01 MPa for 40 days after seeding. Afterward, the experimental units were divided into two groups: in one group the potential was kept at 0.01 MPa, and in the other one, at -0.10 MPa. Sol I water potential was control led gravimetrically twice a day with water replacement until the desired potential was reestablished. A week before harvesting, the leaf water potential (psi), the photosynthetic rate (A), the stomatal conductance (gs) and the transpiration rate were evaluated. The last week before harvesting, the mass of the containers was recorded daily before watering to determine the consumption of water by the plants. After harvesting, total dry matter and leaf area were evaluated. the data were Submitted to analysis of variance, to Tukey's tests and regression analyses. The application of K influenced A, gs and the transpiration rate. Plants deficient in K showed lower A and higher Us and transpiration rates. There were no statistical differences in A, gs and transpiration rates ill plants with and Without water deficit. The addition of K reduced the consumption of water per unit of leaf area and, in general, plants submitted to water deficit presented a lower consumption of water.

Dynamic transitions in a three dimensional associating lattice gas model

The aggregation of interacting Brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the concentration range considered. By generalizing Kramers' rate theory to the presence of shear and collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.

Hydrogen bond interactions between acetone and supercritical water

Hydrogen bond interactions between acetone and supercritical water are investigated using a combined and sequential Monte Carlo/quantum mechanics (S-MC/QM) approach. Simulation results show a dominant presence of con. gurations with one hydrogen bond for different supercritical states, indicating that this specific interaction plays an important role on the solvation properties of acetone in supercritical water. Using QM MP2/aug-cc-pVDZ the calculated average interaction energy reveals that the hydrogen-bonded acetone-water complex is energetically more stable under supercritical conditions than ambient conditions and its stability is little affected by variations of temperature and/or pressure. All average results reported here are statistically converged.

Liquid polymorphism, order-disorder transitions and anomalous behavior: A Monte Carlo study of the Bell-Lavis model for water

The Bell-Lavis model for liquid water is investigated through numerical simulations. The lattice-gas model on a triangular lattice presents orientational states and is known to present a highly bonded low density phase and a loosely bonded high density phase. We show that the model liquid-liquid transition is continuous, in contradiction with mean-field results on the Husimi cactus and from the cluster variational method. We define an order parameter which allows interpretation of the transition as an order-disorder transition of the bond network. Our results indicate that the order-disorder transition is in the Ising universality class. Previous proposal of an Ehrenfest second order transition is discarded. A detailed investigation of anomalous properties has also been undertaken. The line of density maxima in the HDL phase is stabilized by fluctuations, absent in the mean-field solution. (C) 2009 American Institute of Physics. [doi:10.1063/1.3253297]

Dynamic transitions in a two dimensional associating lattice gas model

Using Monte Carlo simulations we investigate some new aspects of the phase diagram and the behavior of the diffusion coefficient in an associating lattice gas (ALG) model on different regions of the phase diagram. The ALG model combines a two dimensional lattice gas where particles interact through a soft core potential and orientational degrees of freedom. The competition between soft core potential and directional attractive forces results in a high density liquid phase, a low density liquid phase, and a gas phase. Besides anomalies in the behavior of the density with the temperature at constant pressure and of the diffusion coefficient with density at constant temperature are also found. The two liquid phases are separated by a coexistence line that ends in a bicritical point. The low density liquid phase is separated from the gas phase by a coexistence line that ends in tricritical point. The bicritical and tricritical points are linked by a critical lambda-line. The high density liquid phase and the fluid phases are separated by a second critical tau-line. We then investigate how the diffusion coefficient behaves on different regions of the chemical potential-temperature phase diagram. We find that diffusivity undergoes two types of dynamic transitions: a fragile-to-strong transition when the critical lambda-line is crossed by decreasing the temperature at a constant chemical potential; and a strong-to-strong transition when the critical tau-line is crossed by decreasing the temperature at a constant chemical potential.

The isotropic nuclear magnetic shielding constants of acetone in supercritical water: A sequential Monte Carlo/quantum mechanics study including solute polarization

The nuclear isotropic shielding constants sigma((17)O) and sigma((13)C) of the carbonyl bond of acetone in water at supercritical (P=340.2 atm and T=673 K) and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP/6-311++G(2d,2p) method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges (electrostatic embedding). In supercritical water, there is a decrease in the magnitude of sigma((13)C) but a sizable increase in the magnitude of sigma((17)O) when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for sigma((17)O) in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP/6-311++G(2d,2p) calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a (13)C chemical shift of 11.7 +/- 0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9-11 ppm. (C) 2008 American Institute of Physics.

Frustration and anomalous behavior in the Bell-Lavis model of liquid water

We have reconsidered the Bell-Lavis model of liquid water and investigated its relation to its isotropic version, the antiferromagnetic Blume-Emery-Griffiths model on the triangular lattice. Our study was carried out by means of an exact solution on the sequential Husimi cactus. We show that the ground states of both models share the same topology and that fluid phases (gas and low- and high-density liquids) can be mapped onto magnetic phases (paramagnetic, antiferromagnetic, and dense paramagnetic, respectively). Both models present liquid-liquid coexistence and several thermodynamic anomalies. This result suggests that anisotropy introduced through orientational variables play no specific role in producing the density anomaly, in agreement with a similar conclusion discussed previously following results for continuous soft core,models. We propose that the presence of liquid anomalies may be related to energetic frustration, a feature common to both models.

Reverse engineering in many-body quantum physics: Correspondence between many-body systems and effective single-particle equations

The mapping, exact or approximate, of a many-body problem onto an effective single-body problem is one of the most widely used conceptual and computational tools of physics. Here, we propose and investigate the inverse map of effective approximate single-particle equations onto the corresponding many-particle system. This approach allows us to understand which interacting system a given single-particle approximation is actually describing, and how far this is from the original physical many-body system. We illustrate the resulting reverse engineering process by means of the Kohn-Sham equations of density-functional theory. In this application, our procedure sheds light on the nonlocality of the density-potential mapping of density-functional theory, and on the self-interaction error inherent in approximate density functionals.

Determination of parathion and carbaryl pesticides in water and food samples using a self assembled monolayer/acetylcholinesterase electrochemical biosensor

An acetylcholinesterase (AchE) based amperometric biosensor was developed by immobilisation of the enzyme onto a self assembled modified gold electrode. Cyclic voltammetric experiments performed with the SAM-AchE biosensor in phosphate buffer solutions ( pH = 7.2) containing acetylthiocholine confirmed the formation of thiocholine and its electrochemical oxidation at E-p = 0.28 V vs Ag/AgCl. An indirect methodology involving the inhibition effect of parathion and carbaryl on the enzymatic reaction was developed and employed to measure both pesticides in spiked natural water and food samples without pre-treatment or pre-concentration steps. Values higher than 91-98.0% in recovery experiments indicated the feasibility of the proposed electroanalytical methodology to quantify both pesticides in water or food samples. HPLC measurements were also performed for comparison and confirmed the values measured amperometrically.