Sulfide (H2S) Corrosion Modeling of Cr-Doped Iron (Fe) Using a Molecular Modeling Approach.

This work presents the use of density functional theory to study the adsorption/dissociation mechanism of the H2S molecule at the Cr-doped iron (Fe(100)) surface. It is observed that H2S is weakly adsorbed on Cr-doped Fe; however, the dissociated products are strongly chemisorbed. The most feasible path for disassociation of HS is favorable at Fe compared to Cr-doped Fe. This study also shows that H2S dissociation is a kinetically facile process, and the hydrogen diffusion follows the tortuous path. This study helps better understand the sulfide corrosion mechanism and its impact, which would help design effective corrosion prevention coatings.

Removal of copper from sulfate solutions using biochar derived from crab processing by-product.

Increasing metal demand is accelerating the mining and processing of minerals, however to ensure sustainable growth innovative approaches are required to better manage associated effluents. Biochar from the fast pyrolysis of residues from fishery and forestry operations has been studied as a low-cost, environmentally and economically friendly method for treating mine tailings and processing effluents. However, the bulk of the studies focus on terrestrial biomass (e.g. wood) and do not include potential inhibition/enhancement of adsorption due to pH controlling compounds. In this work biochar generated from snow crab (Chionoecetes Opilio) processing was studied as an adsorbent for copper solutions containing sulfate (a key compound in sulfide ore mining waters) with the objective of assessing adsorption capacity and the impact of sulfate on copper adsorption. The biochar, a porous structure comprised of calcite (CaCO3), was alkaline and has a negative zeta potential under neutral and basic conditions. The crab biochar removed over 99% of Cu2+ from a 100 mg/L solution (sourced as CuSO4) at a dosage of 5 g/L, which was higher than lignocellulosic biochar at the same biochar dosage. While metal adsorption can often be impacted at acidic conditions, Cu2+ adsorption was not impacted by initial acidic pH due to the biochar's buffering capacity. The Pseudo-Second Order (PSO) model fit the adsorption rate with maximum adsorption achieved in approximately 2 h. The maximum adsorption isotherm capacity was 184.8 ± 10.2 mg/g for Cu2+, much higher than existing commercial activated carbons and previously studied lignocellulosic biochars and followed the Freundlich isotherm. The adsorption mechanism responsible for removal of Cu2+ was found to be precipitation, in the form of the mineral posnjakite (Cu4[(OH)6SO4]·H2O). These results indicate for the first time that crab-based biochars are capable of adsorbing large quantities of Cu2+ from sulfate-rich solution, while also buffering solution pH, demonstrating promise as an acid mine drainage treatment for removal of harmful metals and reduction of acidity.

Shrimp Oil Extracted from Shrimp Processing By-Product Is a Rich Source of Omega-3 Fatty Acids and Astaxanthin-Esters, and Reveals Potential Anti-Adipogenic Effects in 3T3-L1 Adipocytes.

The province of Newfoundland and Labrador, Canada, generates tons of shrimp processing by-product every year. Shrimp contains omega (n)-3 polyunsaturated fatty acids (PUFA) and astaxanthin (Astx), a potent antioxidant that exists in either free or esterified form (Astx-E). In this study, shrimp oil (SO) was extracted from the shrimp processing by-product using the Soxhlet method (hexane:acetone 2:3). The extracted SO was rich in phospholipids, n-3 PUFA, and Astx-E. The 3T3-L1 preadipocytes were differentiated to mature adipocytes in the presence or absence of various treatments for 8 days. The effects of SO were then investigated on fat accumulation, and the mRNA expression of genes involved in adipogenesis and lipogenesis in 3T3-L1 cells. The effects of fish oil (FO), in combination with Astx-E, on fat accumulation, and the mRNA expression of genes involved in adipogenesis and lipogenesis were also investigated. The SO decreased fat accumulation, compared to untreated cells, which coincided with lower mRNA expression of adipogenic and lipogenic genes. However, FO and FO + Astx-E increased fat accumulation, along with increased mRNA expression of adipogenic and lipogenic genes, and glucose transporter type 4 (Glut-4), compared to untreated cells. These findings have demonstrated that the SO is a rich source of n-3 PUFA and Astx-E, and has the potential to elicit anti-adipogenic effects. Moreover, the SO and FO appear to regulate adipogenesis and lipogenesis via independent pathways in 3T3-L1 cells.

Sulfate removal using colloid-enhanced ultrafiltration: performance evaluation and adsorption studies.

Colloid-enhanced ultrafiltration (CEUF), i.e., micellar-enhanced ultrafiltration (MEUF) and polymer-enhanced ultrafiltration (PEUF), was investigated to remove sulfate ions from aqueous solution in batch experiments, using cetyltrimethylammonium (CTAB) and poly(diallydimethylammonium chloride) (PDADMAC) as colloids, respectively. Ultrafiltration performance was evaluated under different initial concentrations of sulfate (0-20 mM) and CTAB/PDADMAC (0-100 mM). The highest retention rate (> 99%) was found in dilute sulfate solutions. At high sulfate concentrations (e.g., 10 mM), a dosage of 50 mM CTAB or PDADMAC can retain approximately 90% of sulfate ions. Though concentration polarization behavior was observed, membrane characterization indicated that the fouling was reversible and membranes can be reused. Furthermore, adsorption equilibrium and kinetics studies show that Freundlich isotherm and pseudo-second-order kinetics can describe the sulfate-colloid interaction, indicating that the surface of absorbents are heterogeneous and the rate-controlling step is chemisorption. Both MEUF and PEUF show potential as effective separation techniques in removing sulfate from aqueous solutions. Under the same conditions examined, PEUF shows advantages over MEUF in its higher retention at lower polymer-to-sulfate ratios, cleaner effluent, and higher adsorption capacity, but compromises on severer flux decline and a tendency of membrane fouling. To overcome this disadvantage, membranes with higher molecular weight cut-off can be used.

Synthesis of a Renewable, Waste-Derived Nonisocyanate Polyurethane from Fish Processing Discards and Cashew Nutshell-Derived Amines.

Waste-derived fish oil (FO) can be epoxidized and reacted with CO2 to produce a cyclic carbonate containing material. Upon reaction with a bioderived amine, this leads to the formation of nonisocyanate polyurethane materials. The FO used is extracted from the by-products produced at fish processing plants, including heads, bones, skin, and viscera. Three different methods are used for the epoxidation of the FO: (i) oxidation by 3-chloroperoxybenzoic acid, (ii) oxidation by hydrogen peroxide and acetic acid, catalyzed by sulfuric acid, and (iii) oxidation by hydrogen peroxide catalyzed by formic acid. Synthesized FO epoxides are reacted with CO2 to yield FO cyclic carbonates with high conversions. The products are characterized by 1 H and 13 C NMR spectroscopy, IR spectroscopy, thermogravimetric analysis, and viscometry. Using a biomass-derived amine, nonisocyanate polyurethane materials are synthesized. This process can lead to new opportunities in waste management, producing valuable materials from a resource that is otherwise underutilized.

Assessment of cross-reactivity in a tailor-made molecularly imprinted polymer for phenolic compounds using four adsorption isotherm models.

Cross-reactivity is an important feature of molecularly imprinted polymers (MIPs), and is central to successful use of a pseudo-template in molecular imprinting. The adsorption and cross-reactivity of a molecularly imprinted polymer (MIP) designed for recognition of phenols from water was assessed using four different isotherm models (Langmuir (LI), Freundlich (FI), Langmuir-Freundlich (L-FI), and Brunauer, Emmett, and Teller (BET)). The L-FI model succeeded in explaining the cross-reactivity behavior through the total number of binding sites, the affinity constants and heterogeneity indices of the small phenols (phenol (ph), 2-methylphenol (2-MP), 3-methylphenol (3-MP), 2-chlorophenol (2-CP), 2,4-dimethylphenol (DMP), 2,4-dichlorophenol (DCP), 4-chloro-3-methylphenol (CMP)) with evidence that the phenols compete for binding sites based on their hydrophobicity as well as π-π, π-σ and dipole-dipole intermolecular forces. The recognition of the large phenols (2,4,6-trichlorophenol (TCP), pentachlorophenol (PCP), 4-teroctylphenol (4-OP), 4-nonylphenol (4-NP), which have much higher binding affinities than the smaller phenolic compounds, was explained with the BET isotherm model that predicts that multiple layers adsorb to the adsorbed monolayer. The adsorption behavior with MIPs is also shown to be superior to corresponding non-imprinted polymers and applicability of MIPs for trace analysis is highlighted.

Comparison of Four Adsorption Isotherm Models for Characterizing Molecular Recognition of Individual Phenolic Compounds in Porous Tailor-Made Molecularly Imprinted Polymer Films.

A molecularly imprinted polymer (MIP) film using catechol as the template was designed for adsorption of a range of phenols from water. Four different isotherm models (Langmuir (LI), Freundlich (FI), Langmuir-Freundlich (L-FI), and Brunauer, Emmett, and Teller (BET)) were used to study the MIP adsorption of five phenolic compounds: phenol (Ph), 2-methylphenol (2-MP), 3-methylphenol (3-MP), 2-chlorophenol (2-CP), and 4-teroctylphenol (4-OP). Each model was evaluated for its fit with the experimental data, and key parameters, including a number of binding sites and binding site energies, were compared. Though the LI, L-FI, and BET models showed good agreement for estimation of the number of binding sites and affinity for most adsorbates, no single model was suitable for all. The LI and L-FI models gave the best fitting statistics for the Ph, 2-MP, 3-MP, and 2-CP. The recognition of 4-OP, which has much higher binding affinities than the smaller phenolic compounds not attributable to hydrophobicity alone, was explained only by the BET model, which indicates the formation of multilayers. The BET model failed only with phenol. MIPs also showed higher adsorption capacities and improved homogeneity over the analogous non-imprinted polymers.

Application of biochar for acid gas removal: experimental and statistical analysis using CO2.

Acid gases such as carbon dioxide and hydrogen sulfide are common contaminants in oil and gas operations, landfill gases, and exhaust stacks from power plants. While there are processes currently used to treat these effluents (e.g., amine absorption and adsorption using zeolite), many of these processes require high energy, space, and hazardous chemicals. Removal using biochar derived from the fast pyrolysis of forestry residues represents a more sustainable option. In this study, adsorption using CO2 as a surrogate for acid gases was investigated using various biochars produced from fast pyrolysis of sawmill residues. Response surface methodology was used to determine operating conditions for maximum adsorption and assess interaction of the adsorption parameters, i.e., temperature, inlet feed flow rate, and CO2 concentration, on biochar adsorption capacity. The Freundlich isotherm best represented the equilibrium adsorption, and the kinetic model was pseudo first-order. Thermodynamic analysis indicated the adsorption process was spontaneous and exothermic. The biochar had better adsorption capacity relative to commercial zeolite. Our results suggested that biochar could be used as a sustainable and cost-effective option for contaminant removal from acid gases produced in landfill gas treatment, fossil fuel extraction, and/or combustion.

Optimization of biosurfactant production by Bacillus Subtilis N3-1P using the brewery waste as the carbon source.

Biosurfactants are biologically produced by microorganisms and therefore biodegradable, making ideal substitutes to chemical surfactants for various applications. Large scale production of biosurfactants is limited because of the high cost. The production cost could be reduced by optimizing cultural conditions and using wastes as substrates. In this work, the response surface methodology (RSM) was used to optimize biosurfactant production by Bacillus subtilis N3-1P strain using brewery waste as the sole carbon source. Five independent variables were varied; carbon and nitrogen concentration, agitation speed, temperature and initial pH. Surface tension and emulsification index were used to measure biosurfactant production. Results indicated that the 'best' surface tension and emulsification index were 27.31 mN m-1 and 63.11%, respectively, under optimized cultural conditions (7% (v v-1) brewery waste, 6.22 g L-1 ammonium nitrate, initial pH of 6.41, 150 rpm, and 27°C). The predicted responses were validated experimentally under the 'optimum' conditions, and 657 mg L-1 of biosurfactant was produced with a critical micelle concentration of 107 mg L-1.

Offshore produced water management: A review of current practice and challenges in harsh/Arctic environments.

Increasing offshore oil and gas exploration and development in harsh/Arctic environments require more effective offshore produced water management, as these environments are much more sensitive to changes in water quality than more temperate climates. However, the number and scope of studies of offshore produced water management in harsh/Arctic environments are limited. This paper reviews the current state of offshore produced water management, impacts, and policies, as well as the vulnerability, implications and operational challenges in harsh/Arctic environments. The findings show that the primary contaminant(s) of concern are contained in both the dissolved oil and the dispersed oil. The application of emerging technologies that can tackle this issue is significantly limited by the challenges of offshore operations in harsh/Arctic environments. Therefore, there is a need to develop more efficient and suitable management systems since more stringent policies are being implemented due to the increased vulnerability of harsh/Arctic environments.

Development, optimization, validation and application of faster gas chromatography - flame ionization detector method for the analysis of total petroleum hydrocarbons in contaminated soils.

This paper presents an important new approach to improving the timeliness of Total Petroleum Hydrocarbon (TPH) analysis in the soil by Gas Chromatography - Flame Ionization Detector (GC-FID) using the CCME Canada-Wide Standard reference method. The Canada-Wide Standard (CWS) method is used for the analysis of petroleum hydrocarbon compounds across Canada. However, inter-laboratory application of this method for the analysis of TPH in the soil has often shown considerable variability in the results. This could be due, in part, to the different gas chromatography (GC) conditions, other steps involved in the method, as well as the soil properties. In addition, there are differences in the interpretation of the GC results, which impacts the determination of the effectiveness of remediation at hydrocarbon-contaminated sites. In this work, multivariate experimental design approach was used to develop and validate the analytical method for a faster quantitative analysis of TPH in (contaminated) soil. A fractional factorial design (fFD) was used to screen six factors to identify the most significant factors impacting the analysis. These factors included: injection volume (µL), injection temperature (°C), oven program (°C/min), detector temperature (°C), carrier gas flow rate (mL/min) and solvent ratio (v/v hexane/dichloromethane). The most important factors (carrier gas flow rate and oven program) were then optimized using a central composite response surface design. Robustness testing and validation of model compares favourably with the experimental results with percentage difference of 2.78% for the analysis time. This research successfully reduced the method's standard analytical time from 20 to 8min with all the carbon fractions eluting. The method was successfully applied for fast TPH analysis of Bunker C oil contaminated soil. A reduced analytical time would offer many benefits including an improved laboratory reporting times, and overall improved clean up efficiency. The method was successfully applied for the analysis of TPH of Bunker C oil in contaminated soil.

Thermal stability investigation of sulfide minerals in DSC.

The safe mining of sulfide ores requires knowledge of the stability/reactivity of the ores under a variety of conditions. This is a large part due to the oxidative self-heating behavior of these ores. In this study, an advanced kinetic simulation approach was used to evaluate the oxidative self-heating of sulfide-mineral concentrate. Kinetic parameters were determined on the basis of non-isothermal DSC measurements at different heating rates by Friedman and ASTM-E698 methods. The estimated kinetic parameters were employed to predict reaction progress under different temperature regimes. The calculated and experimental isothermal profiles suggest an autocatalytic behavior for mineral concentrate oxidation. The precise prediction of reaction rates/progress by an advanced kinetic-based simulation approach in this study is critical from a safe storage and handling perspective.

Sustainable development of process facilities: state-of-the-art review of pollution prevention frameworks.

Pollution prevention (P2) strategy is receiving significant attention in industries all over the world, over end-of-pipe pollution control and management strategy. This paper is a review of the existing pollution prevention frameworks. The reviewed frameworks contributed significantly to bring the P2 approach into practice and gradually improved it towards a sustainable solution; nevertheless, some objectives are yet to be achieved. In this context, the paper has proposed a P2 framework 'IP2M' addressing the limitations for systematic implementation of the P2 program in industries at design as well as retrofit stages. The main features of the proposed framework are that, firstly, it has integrated cradle-to-gate life cycle assessment (LCA) tool with other adequate P2 opportunity analysis tools in P2 opportunity analysis phase and secondly, it has re-used the risk-based cradle-to-gate LCA during the environmental evaluation of different P2 options. Furthermore, in multi-objective optimization phase, it simultaneously considers the P2 options with available end-of-pipe control options in order to select the sustainable environmental management option.