Using innovative copper-loaded activated alumina (Cu/AA) as the catalyst for catalytic wet peroxidation (CWPO) of catechol.

In this study, copper-loaded activated alumina (Cu/AA) was synthesized and used for the CWPO of catechol (a representative refractory organic pollutant). Various characterization techniques were deployed to characterize the catalysts, e.g., activated alumina (AA), as well as pristine and spent 1% Cu/AA. The innovative 1% Cu/AA catalyst exhibited good thermal stability up to 1173 K with a marginal weight loss of 13%. The Cu species were well dispersed on the activated alumina framework with no significant cluster formation. Typically, the average copper particle size of 5 nm was dispersed on the AA framework. Catechol removal was observed to be 92% with 87% mineralization at optimized conditions (initial catechol concentration = 200 mg/L, catalyst dose of 1% Cu/AA = 2 g/L; temperature = 323 K; pH = 6; and H2O2/catechol stoichiometric ratio = 0.5). The mineralization of catechol was analyzed using mass spectroscopy, with the associated mechanism has been elucidated. Results of this study indicated that synthesized catalyst has phenomenal advantages in terms of simple separation and high removal efficiency of catechol, suggesting the feasibility of employing Cu/AA as the effective catalyst for the CWPO of catechol.

Insight into the role and mechanism of polysaccharide in polymorphous magnesium oxide nanoparticle synthesis for arsenate removal.

The low cost and non-toxic of magnesium oxides make it a potential eco-friendly material for arsenic removal. Polysaccharide is a kind of green modifier to obtain nanoscale MgO particles with a higher adsorption affinity. In this study, the impact of chain structures of polysaccharides on the morphology features and arsenate removal efficiency of MgO-NPs were investigated. Pullulan and starch facilitated the synthesis of flower-like MgO-NPs, and pectin facilitated the synthesis of plate-like ones. Although the two kinds of flower-like MgO-NPs undergone similar time to reach equilibrium, the one obtained from the starch-synthesis route showed a higher arsenate adsorption capacity (98 mg g-1), due to that their bushy and smaller petals on the surface provide more active sites for arsenic adsorption. The pectin-synthesis route also produced MgO-NPs with higher arsenate adsorption capacity (101 mg g-1), ascribed to stacking of nano-plates on their surfaces facilitated to form defect surfaces. However, due to their lower BET area, the plate-like MgO-NPs took twice times to reach equilibrium for arsenic adsorption compared with the others. In the stage for the hydrolysis of MgO, hydroxyl groups on the polymer chain provide active sites to physically trap or bond with MgO particles and then to produce hydrolyzed precursors. The poly chain containing inter- and intra-hydroxyl groups directed MgO molecular growing into hydroxide crystals with 3D frameworks during their nucleation and growth. However, pectin only provides inter-hydroxyl groups and directs to form hydroxides with 2D frameworks. Furthermore, the rapid-nucleation vs. slow-growth model in the stage of pyrolysis of hydroxide crystals successfully interprets the thinner petals and complex chemical phases of the final nanoparticles obtained from the pullulan-synthesis route. This work may provide direction and perspectives for the rational design of well-performing MgO materials for arsenate removal.

Bioremediation of trichloroethylene-polluted groundwater using emulsified castor oil for slow carbon release and acidification control.

In this study, the emulsified castor oil (ECO) substrate was developed for a long-term supplement of biodegradable carbon with pH buffering capacity to anaerobically bioremediate trichloroethylene (TCE)-polluted groundwater. The ECO was produced by mixing castor oil, surfactants (sapindales and soya lecithin [SL]), vitamin complex, and a citrate/sodium phosphate dibasic buffer system together for slow carbon release. Results of the emulsification experiments and microcosm tests indicate that ECO emulsion had uniform small droplets (diameter = 539 nm) with stable oil-in-water characteristics. ECO had a long-lasting, dispersive, negative zeta potential (-13 mv), and biodegradable properties (viscosity = 357 cp). Approximately 97% of TCE could be removed with ECO supplement after a 95-day operational period without the accumulation of TCE dechlorination byproducts (dichloroethylene and vinyl chloride). The buffer system could neutralize acidified groundwater, and citrate could be served as a primary substrate. ECO addition caused an abrupt TCE adsorption at the initial stage and the subsequent removal of adsorbed TCE. Results from the next generation sequences and real-time polymerase chain reaction (PCR) indicate that the increased microbial communities and TCE-degrading bacterial consortia were observed after ECO addition. ECO could be used as a pH-control and carbon substrate to enhance anaerobic TCE biodegradation effectively. PRACTITIONER POINTS: Emulsified castor oil (ECO) contains castor oil, surfactants, and buffer for a slow carbon release and pH control. ECO can be a long-term carbon source for trichloroethylene (TCE) dechlorination without causing acidification. TCE removal after ECO addition is due to adsorption and reductive dechlorination mechanisms.

Nutrient removal from domestic wastewater: A comprehensive review on conventional and advanced technologies.

Nitrogen and phosphorous are indispensable for growth and vitality of living beings, hence termed as nutrients. However, discharge of nutrient rich waste streams to aquatic ecosystems results in eutrophication. Therefore, nutrient removal from wastewater is crucial to meet the strict nutrient discharge standards. Similarly, nutrient recovery from waste streams is vital for the realization of a circular economy by avoiding the depletion of finite resources. This manuscript presents analysis of existing information on different conventional as well as advanced treatment technologies that are commonly practiced for the removal of nutrient from domestic wastewater. First, the information pertaining to the biological nutrient removal technologies are discussed. Second, onsite passive nutrient removal technologies are reviewed comprehensively. Third, advanced nutrient removal technologies are summarized briefly. The mechanisms, advantages, and disadvantages of these technologies along with their efficiencies and limitations are discussed. An integrated approach for simultaneous nutrient removal and recovery is recommended. The fifth section of the review highlights bottlenecks and potential solutions for successful implementation of the nutrient removal technologies. It is anticipated that the review will offer an instructive overview of the progress in nutrient removal and recovery technologies and will illustrate necessity of further investigations for development of efficient nutrient removal and recovery processes.

Recent progress in g-C3N4, TiO2 and ZnO based photocatalysts for dye degradation: Strategies to improve photocatalytic activity.

Water contamination by dyes is a matter of concern for human health and the environment. Various methods (membrane separation, coagulation and adsorption) have been explored to remove/degrade dyes. However, now the exploitation of semiconductor assisted materials using renewable solar energy has emerged as a potential candidate to resolve the issue. Although, single component photocatalysts (ZnO, TiO2, ZrO2) were experimented, due to their low efficiency and stability due to the high recombination rate electron-hole pair and inefficient visible light absorption, composites of semiconductor materials are being used. Semiconductor heterojunction systems are developed by coupling two or more semiconductor components. The synergistic effect of their properties, such as adsorption and improved charge carrier migration, is observed to increase overall stability. This review covers recent progress in advanced nanocomposite materials based on g-C3N4, TiO2 and ZnO used as photocatalysts with details of enhancing the photocatalytic properties by heterojunctions, crystallinity and doping. The conclusion at the end displays a summary, research gaps and future outlook. A holistic analysis of recent progress to demonstrate the efficient heterojunctions for photodegradation with optimal conditions, this review will be helpful for the development of efficient heterostructured systems for photodegradation. This review covers references from the year 2017-2020.

Phosphorus removal and recovery from water with macroporous bead adsorbent constituted of alginate-Zr4+ and PNIPAM-interpenetrated networks.

Currently, there is a growing trend in employing natural biomaterials (e.g., alginate) to prepare a novel bead adsorbent for phosphorus (P) elimination. However, the utilization of alginate beads to remove and recover P from effluents possesses limitations associated with its physical characteristics such as a dense gel layer, poor mechanical strength and low stability. To overcome the limitations and improve the adsorption performances, we synthesized a novel alginate-derived bead constituted of PNIPAM network interpenetrated in alginate-Zr4+ network (PNIPAM/SA-Zr) decorated with polyethylene glycol as a pore-forming agent, and then investigated its ability to remove and recover P from effluents. The morphology, functional groups, surface area, and mechanical strength of the beads were evaluated by SEM, FTIR, BET, and swelling analysis. The adsorption of P was investigated by varying various factors. The adsorption kinetics, isotherms, and thermodynamics were studied. Particularly, the P-loaded beads exhibited a faster desorption rate under thermal stimulus, and remained good desorption efficiency and reusability within five consecutive cycles. Zeta-potential and XPS results revealed that the adsorption mechanisms were related to electrostatic interactions, ligand exchange, and the formation of inner-sphere complexes. The beads possessed favorable fixed-bed column operation performances for P removal and recovery from real wastewater.

The activated iron system for phosphorus recovery in aqueous environments.

Finding a good sorbent for phosphorus (P) recovery from the aquatic environment is critical for preventing eutrophication and providing P resources. The activated iron system (mainly consisted of zero-valent iron (ZVI), Fe3O4 and Fe2+) has been reported to exhibit a favorable performance towards various contaminants in wastewater, but its effect on P recovery has not been studied systematically. In this study, we used Fe2+-nitrate pretreatment reaction to prepare the activated iron system and then applied it to P recovery. Results show that more than 99% P was removed from water in 60 min; co-existing anions (NO3-, Cl- and SO42-) and natural organic matter (NOM) had little effect on P removal. The P removal capacity of activated iron system is very high compared with currently reported sorbents. Externally-supplied Fe2+ plays an important role on P removal in the system. Regeneration study shows that the activated iron system exhibited stable P recovery ability by using 0.1 M NaOH solution. Various methods were applied to characterize the ZVI and iron corrosion, and results conclude that sorption precipitation, and co-precipitation contribute to P removal. This method will be promising and have an application potential in the field for efficient and cost-effective recovery of P with cheap microscale zero valent iron.

Simultaneous removal of nitrogen and phosphorus by cetylpyridinium bromide modified zeolite.

In this study, surfactant modified zeolite-clinoptilolite (SMZ) by CPB (cetylpyridinium bromide) was used for simultaneous removal of ammonium, nitrate and phosphate in synthetic wastewater, and the sorption properties of SMZ were determined and compared with natural zeolite. Results showed that natural clinoptilolite had good affinity for ammonium (8.940 mg/g), but not for nitrate (0.427 mg/g) and phosphate (0.801 mg/g). With the increase of surfactant loading from 5 g/L to 40 g/L, the sorption capacity for nitrate increased from 0.462 mg/g to 4.661 mg/g. when the surfactant loading is 40 g/L, the SMZ has a phosphate adsorption capacity of 2.119 mg/g. The SMZ had a significant enhancement on nitrate and phosphate sorption, could simultaneously remove ammonium, nitrate and phosphate at specific conditions, with removal efficiency up to 85.2%, 83.1% and 56.7%, respectively. Orthogonal experiments showed that ammonium concentration was the most important factor for ammonium sorption on SMZ. Surfactant loading was the major factor for nitrate and phosphate sorption. With the increase of surfactant loading from 5 g/L to 40 g/L, the sorption capacity for nitrate increased from 0.462 mg/g to 4.661 mg/g. When the surfactant loading is 40 g/L, the SMZ has the best phosphate adsorption capacity 2.119 mg/g. Samples were characterized by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET). Semi-empirical quantum mechanics molecular simulation indicated that electrostatic attraction existed between CPB and dihydrogen phosphate ion. Results indicate that SMZs might have great potential of removing cations and anions simultaneously in the aquatic environment, which is good for eutrophication control and nutrients removal.

Effect of growth promotants on the occurrence of endogenous and synthetic steroid hormones on feedlot soils and in runoff from beef cattle feeding operations.

Supplements and growth promotants containing steroid hormones are routinely administered to beef cattle to improve feeding efficiency, reduce behavioral problems, and enhance production. As a result, beef cattle manure will contain both synthetic steroids as well as a range of endogenous steroids including androgens, estrogens, and progestogens. A two-year controlled study was conducted in which beef cattle were administered steroid hormones via subcutaneous implants and feed additives and the occurrence of 16 endogenous and synthetic steroid hormones and metabolites was evaluated in runoff from beef cattle feedlots and in manure and soil collected from feedlot surfaces. Samples were extracted and analyzed using liquid chromatography tandem mass spectrometryfor metabolites of the synthetic androgen trenbolone acetate, 17α-trenbolone, 17ß-trenbolone, for the nonsteroidal semisynthetic estrogen agonist, α-zearalanol, and the synthetic progesterone melengesterol acetate, as well as a wide range of endogeneous estrogens, androgens, and fusarium metabolites. Synthetic steroids including trenbolone metabolites and melengestrol acetate were detected in fresh manure and in feedlot surface soils from cattle administered synthetic steroids at concentrations up to 55 ± 22 ng/g dry weight (dw) (17α-trenbolone) and 6.5 ± 0.4 ng/g dw (melengesterol acetate). Melengesterol acetate was detected in 6% of runoff samples from feedlots holding cattle administered synthetic steroids at concentrations ranging up to 115 ng/L. The presence of melengesterol acetate in runoff from beef cattle feeding operations has not been previously reported. Synthetic steroids were not detected in manure or runoff from control cattle. A wide range of endogenous hormones were detected in runoff and feedlot surface soils and manure from cattle given synthetic steroids and from control cattle, with no statistically significant differences in concentration. These results indicate that runoff from confined animal production facilities is of environmental and public health concern regardless of the use of growth promotants.

Phosphorus fate and transport in soil columns loaded intermittently with influent of high phosphorus concentrations.

In this study, several columns of different lengths were filled with composite soils sampled from the field at corresponding depths and then loaded intermittently with influent of a high phosphorus concentration to evaluate phosphorus fate and transport in soil. The results indicate that the height of the mass transfer zone, solvent pore velocity, and soil's life expectancy for phosphorus removal increased with depth, while the retained phosphorus per kilogram of soil and the linear adsorption equilibrium coefficient, R, decreased with depth. An equation was developed to link liquid-phase phosphorus with solvent traveling time and soil depth. The results of X-ray diffraction and washout tests indicate that calcium-phosphorus precipitation and/or crystal growth occurred in the columns. The new protocol is useful for evaluation of phosphorus fate and transport in other subsurface systems, because it allows flexible adjustments in hydraulic loadings, feed solution, and sampling schemes.

Effects of long-term wastewater application on chemical properties and phosphorus adsorption capacity in soils of a wastewater land treatment system.

The buildup of phosphorus (P) in the soil is a major factor limiting the operating life of a wastewater land treatment system. In this study, we evaluated changes of chemical properties, P profiles, and adsorption isotherms in the soils of a Muskegon wastewater land treatment system, which has received wastewater for approximately 30 years. It was found that the pH in the 15-cm topsoil increased from approximately 5-6 in 1973 to approximately 7.4-7.8 in 2003; a large amount of salt (e.g., Ca, Mg) in wastewater was adsorbed by the soil; the soil Al content (either exchangeable or oxalate extractable) decreased, while the oxalate-extractable Fe content remained at the same level. Ca-bound P accounted for > or = 70% of the total P adsorbed in the soil. The soil P adsorption capacity increased and was positively correlated with the concentration of exchangeable Ca in the soil. A higher concentration of exchangeable Ca was found in the 15-cm topsoil, where a higher total organic carbon was present. More P was accumulated in the upper soil than in the deeper soil. The adsorption of Ca in wastewater by the soil may extend the life expectancy of the Muskegon land treatment system.

Quantification of oxygen release by bulrush (Scirpus validus) roots in a constructed treatment wetland.

Amount of oxygen released by bulrush (Scirpus validus) roots has been quantified based on the radial oxygen loss (ROL) exhibited by the roots, the number and the length of active lateral roots, and the field plant density. It was found that wetland bulrush contains two types of active lateral roots (showing ROL), viz., laterals of brown and white main roots. The two laterals have distinct oxygen release characteristics. Based on the dissolved oxygen (DO) microprofiles of brown and white laterals, the ROLs were found to be approximately 61 ng O2 cm(-2) root surface min(-1) and approximately 68 ng O2 cm(-2) root surface min(-1), respectively, at bulk 5-day biochemical oxygen demand (BOD5) of 76 mg L(-1). The respective average active root lengths of the brown and the white laterals were approximately 40 and approximately 1676 microm. Based on field and laboratory measurements, the average amount of oxygen released by bulrush was found to be 2.30 mg O2 m(-2) wetland surface d(-1); of this approximately 71% is from the white roots. The results of this study indicate that plants do not release enough oxygen to meet the total oxygen demand of bulk wastewater, and therefore, constructed wetlands should be designed as an anaerobic or an aerobic-anaerobic hybrid system rather than as an aerobic system. However, the results of this study should be viewed in the background of possible errors (including a reactor design flaw), which might have made the measured oxygen release significantly lower than what plant roots actually release. Further studies are needed to quantify wetland plant oxygen release based on micro-scale measurements.