Establishing a water-to-energy platform via dual-functional photocatalytic and photoelectrocatalytic systems: A comparative and perspective review.

Light-driven photocatalytic (PC) and photoelectrocatalytic (PEC) systems are vital technologies being extensively explored for wastewater treatment and energy production. Although the photo(electro)catalytic applications in both the energy production and wastewater remediation function on the similar principle of photo-induced charge transfer, most preceding research has been focused on either the energy recovery or wastewater treatment as these two applications demand distinct reaction parameters and catalyst properties. The present review reveals the scientific progress in dual-functional PC and PEC processes that enable simultaneous energy recovery (e.g., H2 generation) with wastewater treatment (e.g., degradation of organic pollutants). The key concept in the dual-functional photo(electro)catalytic system is to use both the electron reduction power for recovering H2 from wastewater and hole oxidation power for degrading pollutants in wastewater simultaneously. Herein, a detailed and comprehensive overview of the advancement in various PC and PEC processes with dual-functional purpose is discussed, highlighting the advantages and disadvantages of different systems and performance comparison based on diverse metrics tools. Although in its infancy, this dual-functional technology has gained scientific interest over the past few years; this is expected, as this approach can overcome multiple major environmental challenges, such as water scarcity, global warming, and pollution. The review should offer current limitations and prospects for developing next-generation solar-driven dual-functional techniques based on the water-energy nexus.

Statistical study of Khibiny Alkaline Massif (Kola Peninsula) groundwater quality with respect to elevated aluminum concentrations.

Current study addresses a problem of elevated aluminum concentrations deteriorating Khibiny Alkaline Massif groundwater quality. The application of chemometric methods to the field dataset 1999-2018 allows to quantitatively describe the groundwater quality, reveal variability patterns and potential sources of elevated aluminum level in the groundwater. The field dataset contains almost 40% more observations of 12 physicochemical groundwater quality parameters than the dataset analyzed in our previous studies on Khibiny groundwater quality assessment reported in the literature. The results revealed statistically significant (α-level=0.05) associations between Al and pH, Cl-, NO3-, SO42- according to the calculated matrix using distance correlation method. The mathematical models developed with the application of multiple regression and factor/principal component analysis elucidate up to 55.5% Al concentration variability and up to 68.3% of total dataset variance. Calculated for the 19-year period the water quality index values, which changed in early 2000s from fair to a marginal category, still belongs to this category reflecting unsatisfactory water quality conditions. Comparing the current study results to the conclusions drawn in our previous publications it is assumed that the main factors determining substandard groundwater quality have remained the same since last groundwater quality assessment reported in the literature. The examined combination of chemometric methods allows to gain insight into the main features of variability patterns of water quality characteristics and the potential sources of groundwater contamination. This approach forms a reliable foundation for enhancing groundwater quality monitoring and control in the Arctic region of interest and other locations experiencing similar problems.

Combined sewer overflow treatment: Assessing chemical pre-treatment and microsieve-based filtration in enhancing the performance of UV disinfection.

Disinfection of combined sewer overflow (CSO) is necessary to reduce the amount of microorganisms discharged into surface waters. In this study, an efficient and cost-competitive treatment for CSO, employing UV disinfection, was developed. High suspended solids content in CSO poses a significant challenge for UV disinfection so laboratory experiments were carried out to asses the effect of chemical pre-treatment followed by micro-sieve filtration on the reduction of total suspended solids (TSS) and the increase of UV transmittance (UVT). The efficiency of UV, with and without pre-treatment, was investigated and a microbial inactivation model was developed to describe the fecal coliforms (FC) inactivation kinetics. Finally, the environmental impacts of the proposed treatment were simulated at the large-scale by stormwater management model (SWMM), and the cost of the proposed treatment train was evaluated and compared with current CSO treatment strategies. Experimental results showed that UV alone achieved 3.6-log reduction of FC at a UV fluence of 80 mJ/cm2, while a 4-log reduction of FC was achieved at a much lower UV fluence of 10 mJ/cm2, when the UV disinfection was preceded by chemical pre-treatment and microsieving filtration using a 32 µm mesh. Under these conditions, the TSS removal achieved was 73%, and the UVT increased from 14% to 32%.The SWMM showed that the proposed CSO treatment achieved a reduction in TSS by one order of magnitude and a decrease in number of FC from 1.05 × 1014 to 1.24 × 1010 CFU. The cost analysis performed herein suggests that the proposed treatment train is competitive to current CSO treatment strategies in terms of cost-effectiveness. The study demonstrates the potential of the innovative CSO treatment scheme to quickly and effectively treat a large amount of wastewater flow thus providing municipalities with a low footprint treatment unit for CSO.

Inactivation of Murine Norovirus and Fecal Coliforms by Ferrate(VI) in Secondary Effluent Wastewater.

Ferrate(VI) (FeVIO42, Fe(VI)) is an emerging oxidant/disinfectant to treat a wide range of contaminants and microbial pollutants in wastewater. This study describes the inactivation of murine norovirus (MNV) by Fe(VI) in phosphate buffer (PB) and secondary effluent wastewater (SEW). The decay of Fe(VI) had second-order kinetics in PB while Fe(VI) underwent an initial demand followed by first-order decay kinetics in SEW. The Chick-Watson inactivation kinetic model, based on integral CT (ICT) dose, well fitted the inactivation of MNV in both PB and SEW. In PB, the values of the inactivation rate constant (kd) decreased with an increase in pH, which was related to the reaction of protonated Fe(VI) species (HFeO4-) with MNV. Higher kd was observed in SEW than in PB. The inactivation of indigenous fecal coliforms (FC) in SEW was also measured. A two-population double-exponential model that accounted for both dispersed and particle-associated FC well fitted the inactivation data with determined kd and particle-associated inactivation rate constant (kp). Results show that Fe(VI) was more effective in inactivating dispersed FC than MNV. The MNV inactivation results obtained herein, coupled with the detailed modeling, provide important information in designing an Fe(VI) wastewater disinfection process.

Study of aluminium in groundwater using chemometric methods.

The field dataset including physico-chemical characteristics of Khibiny alkaline massif groundwater aquifer was analysed for the first time by applying chemometric methods to explore the relationships between investigated parameters in both time and frequency domains. Elevated Al concentration in water of this aquifer is described as a serious health concern when used for the household water supply. The time series of 12 physico-chemical parameters were examined by using Pearson correlation, multiple linear regression and spectral analysis based on fast Fourier transform (FFT) algorithm. Computed pairwise correlation coefficients matrix revealed that pH values, NO3-, SO42-, Cl- and TDS correlate with Al concentrations at a statistically significant level (α-level = 0.05). The multiple regression model including Cl-, NO3- and pH explains up to 54% of Al concentrations temporal variation in groundwater. Fourier coefficients, power spectral density (PSD) and cumulative spectral power (CSP) were calculated for Al, pH, NO3- and Cl- time series to identify and analyse the strength of their variations as a function of frequency. Calculations revealed the spectrums of these variables include three main frequency bands corresponding approximately to 5-7, 13-17 and 20-34 month periods. The fluctuations within these bands contribute mostly to the total temporal variation of Al, Cl-, NO3- concentrations and pH values.

A microsieve-based filtration process for combined sewer overflow treatment with nutrient control: Modeling and experimental studies.

Combined sewer overflows contain a highly variable, wide range of contaminants, both in particulate and soluble form, making conventional water treatment processes unable to offer adequate public health protection. In this study, an integrated treatment process designed to simultaneously remove typical combined sewer overflow pollutants (suspended solids, chemical oxygen depends, turbidity) in conjunction with nutrient (nitrogen and phosphorus), was developed. The removal of particulates as well as dissolved nitrogen and phosphorus was achieved by first adsorbing soluble pollutants on zeolite and powdered activated carbon, and subsequently applying filtration carried out by polymer-enhanced microsieving. Laboratory experiments were designed using design-of-experiment techniques and carried out to assess the effects of the various treatment variables (cationic polymer, zeolite, powder activated carbon and microsieve size) in the designed combinations. A response surface model was fitted to the experimental dataset in order to capture and describe the non-linear relationships between treatment variables and treatment objectives. Finally, an optimization study was carried out using Pareto analysis showing that cationic polymer, zeolite, and powdered activated carbon, followed by fine mesh microsieving, worked synergistically in the integrated treatment process. Several optimal process conditions emerged, in particular, a treatment combination consisting of 1.1 mg/L of the cationic polymer, 250 mg/L of zeolite, 5 mg/L of powdered activated carbon, and a 370 µm mesh size. Under this condition, expected performance would be reductions of 72%, 56%, 35%, and 75% for turbidity, total Kjeldahl nitrogen, total chemical oxygen demand, and total phosphorous, respectively. The findings presented in this paper demonstrate the possibility of achieving multiple treatment objectives in a single and integrated treatment step, hence providing municipalities with viable treatment options where the issues of combined sewer overflow and nutrient management are simultaneously tackled.

Coagulation and disinfection by-products formation potential of extracellular and intracellular matter of algae and cyanobacteria.

Coagulation and flocculation can remove particulate algal cells effectively; however, they are not very effective for removing dissolved algal organic matter (AOM) in drinking water plants. In this work, optimum coagulation conditions using alum for both extracellular and intracellular organic matter of six different algal and cyanobacterial species were determined. Different coagulation conditions such as alum dosage, pH, and initial dissolved organic carbon (DOC) were tested. Hydrophobicity, hydrophilicty, and transphilicity of the cellular materials were determined using resin fractionation method. The removal of DOC by coagulation correlated well with the hydrophobicity of the AOM. The disinfection by-product formation potential (DBPFP) of various fractions of AOM was determined after coagulation. Although, higher removal occurred for hydrophobic AOM during coagulation, specific DBPFP, which varied from 10 to 147 µg/mg-C was higher for hydrophobic AOM. Of all the six species, highest DBPFP occurred for Phaeodactylum tricornutum, an abundant marine diatom species, but is increasingly found in surface water.

Rapid removal of acesulfame potassium by acid-activated ferrate(VI) under mild alkaline conditions.

Acesulfame potassium (ACE) is a widely used artificial sweetener that has consistently been detected in wastewater and surface waters. The high-valent iron-based green oxidant known as ferrate(VI) (potassium ferrate(VI); Fe(VI)) had low reactivity with ACE (i.e. 4 h (or 240 min) contact time removed only ∼ 67% ACE) at a molar ratio of 6.0 ([Fe(VI)]:[ACE]). Comparatively, it took 60 s (or 1 min) to remove ∼94% ACE when HCl (786 µM) was added to a mixture of Fe(VI)-ACE at the same molar ratio of 6.0 (or acid-activated Fe(VI)). Significantly, the final pH (i.e. 7.6-8.1) was similar for Fe(VI) and acid-activated Fe(VI). An empirical model using response surface methodology was developed that could describe reasonably well the removal efficiency of ACE. Inorganic constituents of wastewater (Cl-, Na+, Ca2+, and Mg2+) had no significant effect on the oxidation of ACE by acid-activated Fe(VI). The degradation efficiency of ACE decreased in the presence of 10 mg/L of natural organic matter (NOM) but remained unchanged at 5 mg NOM/L. Sulfamic acid as the oxidized product of ACE was identified by liquid chromatography high resolution mass spectrometry method. Reaction pathways include ring opening of ACE through hydrolytic transformation. Acid-activated Fe(VI) has advantage of rapid removal of ACE under mild alkaline conditions of wastewater treatment plants compared to other oxidation processes such as chlorination, ozonation, and light-based processes.

Pharmaceuticals and pesticides in secondary effluent wastewater: Identification and enhanced removal by acid-activated ferrate(VI).

The emergence of resistance to antibacterial drugs and pesticides in water is unprecedented. This may have adverse consequences to human health and ecological systems. This paper first sought the identification of a wide range of pharmaceuticals and pesticides in two secondary effluent wastewaters (SEW) of different quality characteristics, followed by their removal by ferrate(VI) (Fe(VI), FeO42-). Screening for 22 pharmaceuticals and 32 pesticides, revealed that 11 pharmaceuticals and 3 pesticides in SEW of plant A, and 14 pharmaceuticals and 5 pesticides in SEW of plant B were present at concentrations higher than the liquid chromatography mass spectrometry method quantitation limit. The concentrations of pharmaceuticals and pesticides ranged from 0.15 ng/L-413.03 ng/L. Investigation of the removal of these pharmaceuticals and pesticides by Fe(VI) showed that some had recalcitrant activity towards their oxidation. Acid-activated Fe(VI) resulted in enhanced oxidation (12.6%-56.2% degradation efficiency) of 6 and 7 pharmaceuticals in SEW of plant A and plant B, respectively, at a shorter time than Fe(VI) without activation (i.e. 3-5 min versus 15-30 min). The degradation of 1 and 3 pesticides in SEW of plant A and plant B respectively, has also been enhanced by activating Fe(VI) (13.8%-86.2% degradation efficiency). Results on testing of organic matter characterization of treated SEW with and without acid-activated Fe(VI) treatment are also presented. Acid-activated Fe(VI) treatment has potential in enhancing the removal of micropollutants in real wastewater.

Solar degradation of diclofenac using Eosin-Y-activated TiO2: cost estimation, process optimization and parameter interaction study.

Diclofenac (DCF), a widely used non-steroidal anti-inflammatory drug, is a commonly detected substance that readily accumulates in tissues of aquatic fish and poses a threat to wildlife and freshwater quality. Advanced Oxidation Processes have been employed as an alternative due to the inadequacy of conventional treatment methods of trace contaminants. This study utilized an innovative method of solar-activation of TiO2 using Eosin-Y dye for the degradation of DCF. Furthermore, the study incorporated a central composite design (CCD) to optimize the dye concentration and estimated the cost for the present process. Optimized parameters for light intensity (750 mW/cm2), Eosin-Y dye concentration (2 mg/L), TiO2 loading (37.5 mg/cm2) and DCF concentration (25 mg/L) were determined through a CCD. The optimized parameters convey a DCF degradation rate of 40% and 49% for 2 ppm (low range) and 4 ppm (high range) dye concentrations, respectively, for a 5-minute reaction time. Cost estimation for the materials used was for the current process was also performed. It was determined that the additional cost of using 4 ppm instead of 2 ppm to achieve only 10% more DCF degradation is not warranted and would require additional treatment to remove subsequently formed halogenated compounds.

Determination of adsorption isotherm parameters for minor whey proteins by gradient elution preparative liquid chromatography.

Ion-Exchange Chromatography (IEC) techniques have been extensively investigated in protein purification processes, due to the more selective and milder separation steps. To date, existing studies of minor whey proteins fractionation in IEC have primarily been conducted as batch uptake studies, which require more experimental search space, time and materials. In this work, the selected resin's (SP Sepharose FF) equilibrium and dynamic binding capacity were first investigated. Next, adsorption of the pure binary mixture of lactoperoxidase and lactoferrin was studied to calibrate steric mass action (SMA) model using a simplified approach with data from single column experiments. The calibrated model was then verified by performing factorial-design based experiments for various process operating conditions assessing process performance on a larger bed height column. The model predicted results demonstrated a realistic agreement with the experiments providing reproducible column elution profile and reduced experimental work. Finally, whey protein isolate was used to evaluate model parameters in real conditions. Results obtained herein are suitable for future large scale applications.

Sacrificial hydrogen generation from aqueous triethanolamine with Eosin Y-sensitized Pt/TiO2 photocatalyst in UV, visible and solar light irradiation.

In this paper, we have studied Eosin Y-sensitized sacrificial hydrogen generation with triethanolamine as electron donor in UV, visible, and solar light irradiation. Aeroxide TiO2 was loaded with platinum metal via solar photo-deposition method to reduce the electron hole recombination process. Photocatalytic sacrificial hydrogen generation was influenced by several factors such as platinum loading (wt%) on TiO2, solution pH, Eosin Y to Pt/TiO2 mass ratio, triethanolamine concentration, and light (UV, visible and solar) intensities. Detailed reaction mechanisms in visible and solar light irradiation were established. Oxidation of triethanolamine and formaldehyde formation was correlated with hydrogen generation in both visible and solar lights. Hydrogen generation kinetics followed a Langmuir-type isotherm with reaction rate constant and adsorption constant of 6.77×10(-6) mol min(-1) and 14.45 M(-1), respectively. Sacrificial hydrogen generation and charge recombination processes were studied as a function of light intensities. Apparent quantum yields (QYs) were compared for UV, visible, and solar light at four different light intensities. Highest QYs were attained at lower light intensity because of trivial charge recombination. At 30 mW cm(-2) we achieved QYs of 10.82%, 12.23% and 11.33% in UV, visible and solar light respectively.

Oxidative protein refolding on size exclusion chromatography at high loading concentrations: fundamental studies and mathematical modeling.

Size exclusion chromatography has been demonstrated as an effective method for refolding a variety of proteins. However, to date process development mainly relies on laboratory experimentation of individual factors. A robust model is essential for high-throughput process screening and optimization of systems to provide higher productivity and refolding yield. In this work, a detailed kinetic scheme of oxidative refolding of a model protein (lysozyme) has been investigated to predict the refolding results in SEC. Non-reactive native, quenched and equilibrium studies were conducted to obtain the model parameters for the species formed during refolding of denatured/reduced lysozyme. The model was tested in various operating conditions, such as: protein loading concentration, injection volume, flow rate and composition of refolding buffer with and without the use of l-arginine additive. An apparent two-state mechanism was found adequate to describe refolding of lysozyme on SEC for the operating condition tested in this work. Furthermore, using low concentration of l-arginine combined with urea as common aggregation suppressor additives showed insignificant change in kinetics of refolding of lysozyme on SEC. However, addition of l-arginine changed mass transfer properties of some of the species formed in refolding reaction which was considered in the model to accurately predict the result of refolding on SEC.

Treatment of combined sewer overflows using ferrate (VI).

This paper presents the results of a study conducted on the treatment of combined sewer overflows using ferrate (VI) [Fe (VI)]. At a Fe (VI) dose of 0.24 mg/L, total chemical oxygen demand (TCOD), soluble chemical oxygen demand (SCOD), total biochemical oxygen demand (TBOD5), soluble biochemical oxygen demand (SBOD5), total suspended solids (TSS), volatile suspended solids (VSS), total phosphorus (TP), total nitrogen (TN), and soluble TN removal efficiencies of 71, 75, 69, 68, 72, 83, 64, 38, and 36%, respectively, were achieved. Kinetic studies revealed that a contact time of only 15 minutes is sufficient to achieve secondary effluent criteria. An innovative technique of using primary sludge (PS) and thickened waste activated sludge as a source for the in situ synthesis of ferrate was developed. A comparative study of treatment efficiencies achieved by Fe (VI) generated from different sources was done. At 0.1 mg/L dose of Fe (VI) synthesized from PS, TCOD, SCOD, TSS, VSS, TP, and TN removal efficiencies of 60, 62, 63, 67, 30, and 25%, respectively, were achieved.

Multi-variable operational characteristic studies of on-column oxidative protein refolding at high loading concentrations.

Chromatographic-based protein refolding techniques have proven to be superior to conventional dilution refolding methods, due to the higher loading concentration and simultaneous purification. Among these techniques, Size Exclusion Chromatography (SEC) has in particular been demonstrated as an effective method for refolding of variety of proteins. To date existing studies of protein refolding at high concentrations (>1mg/mL) in SEC have primarily been conducted as single factor studies, in which a single parameter is varied to assess impact on operating performance, which does not allow for determination of the interactions of different operating parameters and optimized operating conditions. In this work a multi-variable investigation of size exclusion protein refolding at high protein concentration using lysozyme as a model protein was performed, in order to quantify the interaction of factors and optimize performance. It was observed when l-arginine is used as an additive the refolding yield becomes independent of the protein concentration and refolding buffer pH, providing that a redox couple is used to assist the reformation of disulfide bridges. Furthermore, the pore accessibility for small molecules was reduced at the presence of this additive particularly at higher protein concentrations indicating slower removal of these molecules and a possible additional mechanism of aggregation prevention. Using the subsequent optimized refolding buffer, a refolding yield of more than 90% was obtained for up to 40mg/mL loading concentration of lysozyme which has only been reported for a urea gradient SEC (8-2M) with lower equilibration and elution flow rates due to high viscosity of buffer containing high concentrations of urea.

Chromatographic resolution and isotherm determination of (R,S)-mandelic acid on Chiralcel-OD column.

Resolution of racemic mandelic acid ((R,S)-MA) and numerical determination of binary competitive isotherm of (R,S)-MA on Chiralcel-OD column have been investigated in this study. The effects of the alcohol modifier and acidic additive in the mobile phase on the retention and enantioseparation of (R,S)-MA were studied at first. The inverse method was then used to determine the competitive isotherm parameters of (R,S)-MA by minimizing the sum of square deviations of the model predictions from the measured elution profiles. The results indicate that the mobile phase with 85% hexane/15% isopropanol/0.3% trifluoroacetic acid mixture gives the best resolution of (R,S)-MA and competitive-modified Langmuir isotherm provides the more accurate sorption mechanism of (R,S)-MA on the cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase.

Oxidation of X-ray compound ditrizoic acid by ferrate(VI).

Iodinated X-ray contrast media (ICM) such as diatrizoic acid (DTZA) is used in large amounts in hospitals to enhance imaging of organs and blood vessels during radiography. Due to its persistence and non-biodegradability, it is found in treated water, sewage effluent, surface waters, and aquatic environments. This paper presents the kinetics of the oxidation of DTZA by ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) as a function of pH (7.1-9.6) at 25 degrees C in order to determine the effectiveness of Fe(VI) to remove DTZA from water. The reaction was determined to be first-order with respect to concentrations of Fe(VI) and DTZA. The rate of the reaction was found to be pH dependent and the rate decreased nonlinearly as the pH increase from 7.1 to 9.6. The speciation of Fe(VI) (HFeO4(-) and FeO4(2-)) was used to explain the rate dependence on pH. The calculated rate constant of Fe(VI) with DTZA at pH 7.0 was compared with nitrogen-containing pollutants and is briefly discussed.

An innovative approach to synthesize highly-ordered TiO2 nanotubes.

An innovative route to prepare highly-ordered and dimensionally controlled TiO2 nanotubes has been proposed using a mild sonication method. The nanotube arrays were prepared by the anodization of titanium in an electrolyte containing 3% NH4F and 5% H2O in glycerol. It is demonstrated that the TiO2 nanostructures has two layers: the top layer is TiO2 nanowire and underneath is well-ordered TiO2 nanotubes. The top layer can easily fall off and form nanowires bundles by implementing a mild sonication after a short annealing time. We found that the dimensions of the TiO2 nanotubes were only dependent on the anodizing condition. The proposed technique may be extended to fabricate reproducible well-ordered TiO2 nanotubes with large area on other metals.

Photocatalytic degradation of nonionic surfactant, Brij 35 in aqueous TiO2 suspensions.

The photocatalytic oxidation of nonionic surfactant, Brij 35 in aqueous TiO2 suspensions was investigated as a function of catalysts loading, light intensity (I), initial Brij 35 concentration [Brij](0), dissolved oxygen concentration [p(O2)], and pH. A monolithic swirl-flow photoreactor was used that allowed to perform a systematic analysis of rates at various loadings of TiO22 in order to distinguish "kinetic" and "transport" limited regimes for the photocatalytic degradation of Brij 35 in TiO2 suspensions. The optimal catalyst loading was determined to be 0.1 g L(-1) TiO2 at a neutral pH. The true kinetic dependences of the photocatalytic degradation on I and [Brij](0) were determined. A small increase in oxidation rate was observed with an increase in the partial pressure of the oxygen [p(O2)] in the system. The rates as a function of [Brij](0) and [p(O2)] were interpreted using a Langmuir-Hinshelwood model. The complete photocatalytic degradation of Brij 35 was obtained in acidic to basic pH range, however, the removal of Brij 35 removal and subsequent decrease in TOC levels were more efficient at a neutral pH than acidic or basic pH.

The fabrication of highly ordered and visible-light-responsive Fe-C-N-codoped TiO2 nanotubes.

A one-step method for the fabrication of Fe-C-N-codoped TiO2 nanotubes by electrochemical anodization is reported. The proposed method is both simple and efficient. The prepared samples were annealed at 550 degrees C for 3 h. The resulting nanotubes were characterized by SEM, XRD, XPS, EDX and UV-vis spectrophotometer. The results showed that the average tube diameter of the nanotubes was 70 nm and wall thickness was 20 nm and the average tube length was 2.4 microm. The doped TiO2 nanotubes exhibited strong absorption in the visible-light region. The maximum photocurrent efficiency measured under solar simulator was 2.7%.