On-Site Pilot-Scale Microalgae Cultivation Using Industrial Wastewater for Bioenergy Production: A Case Study towards Circular Bioeconomy.

This case study assesses the valorization of industrial wastewater streams for bioenergy generation in an industrial munition facility. On-site pilot-scale demonstrations were performed to investigate the feasibility of algal growth in the target wastewater on a larger outdoor scale. An exploratory field study followed by an optimized one were carried out using two 1000 L open raceway ponds deployed within a greenhouse at an industrial munition facility. An online system allowed for constant monitoring of operational parameters such as temperature, pH, light intensity, and dissolved oxygen within the ponds. The original algal seed evolved into an open-air resilient consortium of green microalgae and cyanobacteria that were identified and characterized successfully. Weekly measurements of the level of nutrients in pond liquors were performed along with the determination of the algal biomass to quantitatively evaluate growth yields. After harvesting algae from the ponds, the biomass was concentrated and evaluated for oil content and biochemical methane potential (BMP) to provide an estimate of the algae-based energy production. Additionally, the correlation among biomass, culturing conditions, oil content, and BMP was evaluated. The higher average areal biomass productivity achieved during the summer months was 23.9 ± 0.9 g/m2d, with a BMP of 350 scc/gVS. An oil content of 22 wt.% was observed during operation under low nitrogen loads. Furthermore, a technoeconomic analysis and life cycle assessment demonstrated the viability of the proposed wastewater valorization scenario and aided in optimizing process performance towards further scale-up.

Oxidative degradation of nitroguanidine (NQ) by UV-C and oxidants: Hydrogen peroxide, persulfate and peroxymonosulfate.

Nitroguanidine (NQ), a component used in insensitive munitions formulations, has high solubility which often leads to highly contaminated wastewater streams. In this work, batch experiments were conducted to investigate and compare the NQ degradation by UV-based advanced oxidation processes (AOPs); hydrogen peroxide (H2O2), persulfate (PS) and peroxymonosulfate (PMS) were selected as oxidants. A preliminary evaluation of AOPs kinetics, byproducts, and potential degradation pathways were carried out and compared to NQ degradation by direct UV-C photolysis. The effects of oxidant dosage, NQ concentrations and pH were evaluated by determining the respective kinetic constants of degradation. Among the treatments applied, UV/PS showed to be a promising and effective alternative leading to faster rates of degradation respect to both oxidant dosage (25 mM) and initial NQ concentrations (≤24 mM). Nevertheless, the degradation rate of NQ by UV/PS appeared to be affected strongly by the initial pH compared to UV/H2O2 and UV/PMS, with the lowest rate overall at pH ≥ 8.0. In addition, the main byproducts from NQ degradation, guanidine and cyanamide, showed to be involved in further degradation steps only with UV/PS and UV/PMS suggesting higher degradation effectiveness of these oxidants compared UV/H2O2 and UV alone.

Load-bearing biodegradable PCL-PGA-beta TCP scaffolds for bone tissue regeneration.

A biocompatible and biodegradable scaffold with load-bearing ability is required to enhance the repair of bone defects by facilitating the attachment, and proliferation of cells, and vascularization during new bone formation. However, it is challenging to maintain the porosity and biodegradability, as well as mechanical properties (especially compressive strength), at the same time. Therefore, in the present work, a biodegradable composite structure of poly(caprolactone) (PCL) was designed using compression molding with varying amounts of poly(glycolic acid) (PGA) (25, 50, 75 wt%) and fixed amount (20 wt%) of beta tricalcium phosphate (beta TCP). It was hypothesized that the fabricated composite structure will develop porosity during the degradation of the PGA and that the corresponding decrease in mechanical properties will be compensated by new bone formation and ingrowth, in vivo. Accordingly, we have systematically studied the effects of sample composition on time-dependent dissolution and mechanical properties of the PGA/beta TCP scaffolds. The compressive strength increased up to ~92 MPa at 50% compression of the designed PCL-PGA samples. Furthermore, the dissolution rate, as well as weight loss, was observed to increase with an increase in the PGA amount in PCL. Based on the mechanical properties and dissolution data, it is concluded that the PCL-PGA scaffolds with beta TCP can be suitable candidates for bone tissue engineering applications, specifically for the reconstruction of bone defects, where strength and biodegradation are both important characteristics.

Load-bearing biodegradable polycaprolactone-poly (lactic-co-glycolic acid)- beta tri-calcium phosphate scaffolds for bone tissue regeneration.

A biodegradable scaffold with tissue ingrowth and load-bearing capabilities is required to accelerate the healing of bone defects. However, it is difficult to maintain the mechanical properties as well as biodegradability and porosity (necessary for bone ingrowth) at the same time. Therefore, in the present study, polycaprolactone (PCL) and poly(lactic-co-glycolic acid) (PLGA5050) were mixed in varying ratio and incorporated with 20 wt.% ßTCP. The mixture was shaped under pressure into originally non-porous cylindrical constructs. It is envisioned that the fabricated constructs will develop porosity with the time-dependent biodegradation of the polymer blend. The mechanical properties will be sustained since the decrease in mechanical properties associated with the dissolution of the PLGA and the formation of the porous structure will be compensated with the new bone formation and ingrowth. To prove the hypothesis, we have systematically studied the effects of samples composition on the time-dependent dissolution behavior, pore formation, and mechanical properties of the engineered samples, in vitro. The highest initial (of as-prepared samples) values of the yield strength (0.021±0.002 GPa) and the Young's modulus (0.829±0.096 GPa) were exhibited by the samples containing 75 wt.% of PLGA. Increase of the PLGA concentration from 25 wt.% to 75 wt.% increased the rate of biodegradation by a factor of 3 upon 2 weeks in phosphate buffered saline (1× PBS). The overall porosity and the pore sizes increased with the dissolution time indicating that the formation of in-situ pores can indeed enable the migration of cells followed by vascularization and bone growth.

Evaluation of metal oxides and activated carbon for lead removal: Kinetics, isotherms, column tests, and the role of co-existing ions.

Activated carbon (AC) is commonly used in faucet and pitcher filters for lead (Pb(II)) removal in homes. This study evaluated the Pb(II) removal performance of AC and metal oxides (e.g. Fe(OH)3 and TiO2), as well as the co-existing ions' effect on Pb(II) removal. Results showed that metal oxides had higher adsorption capacity (28.9-51.5 mg/g) than AC (21.2 mg/g). Pb(II) was inner-spherically adsorbed onto both AC and metal oxides surfaces. Among various metal ions, calcium (Ca(II)) demonstrated dramatic effects on Pb(II) removal ability of AC, while it had no effect on Pb(II) adsorption by metal oxides. This difference resulted from the inner- and outer-sphere adsorption of Ca(II) on AC and metal oxides, respectively. The presence of orthophosphate (orth-P) and sulfate enhanced Pb(II) removal by those three adsorbents, whereas carbonate and silicate had negligible effect on Pb(II) adsorption. Interestingly, while the orth-P was usually used as corrosion inhibitor because of the formation of lead-phosphate coprecipitate, we found that the enhanced effect of orth-P on Pb(II) removal was mainly due to the synergistic adsorption. This study provides valuable information for the selection of effective adsorbents for Pb(II) removal and is helpful for understanding the roles of co-existing ions on it.

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) reduction by granular zero-valent iron in continuous flow reactor.

Wastewater streams containing hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) are subject to regulatory discharge regulations that require processing through industrial waste treatment. Thus, the development of easy-to-apply technologies for the treatment of RDX-laden wastewater streams is imperative. In the present study, the reduction of RDX by granular zero valent iron (GZVI) in batch and column experiments was investigated. Preliminary batch tests conducted under both oxic and anoxic conditions showed that after 3.0 h of reaction with GZVI, RDX was mainly converted to formaldehyde (CH2O), nitrate (NO3-), and ammonium (NH4+). Column filtration tests showed that pretreatment of the GZVI media with acid wash and low influent pH (4.0 ± 0.1) achieved 99% removal of RDX up to 5000 bed volume. BOD tests carried out on the post-treatment streams showed increased biodegradability of the treated wastewater, leading to a lower environmental impact for the final waste.

Effect of phosphate releasing in activated sludge on phosphorus removal from municipal wastewater.

Aluminum and ferric salts are commonly used in municipal wastewater treatment plants (WWPTs) for phosphorus (P) removal. In this study, on-site jar tests were conducted to determine the removal of different P species from the fresh samples in the presence and absence of activated sludge (AS) with different doses of alum, poly-aluminum chloride, and ferric chloride at different pH. The soluble P (SP) concentration in the samples was about 0.63mg/L. When the mixed liquor containing AS was treated with 8mg/L of Al, SP could be reduced to 0.13mg/L, while it was reduced to 0.16mg/L with only 1mg/L of Al after sedimentation removal of AS from sample. Chemical analysis determined that AS contained 59.8mg-P/g-TSS and 43.8mg-Al/g-TSS and most of the P was associated with the aluminum hydroxide. We discovered that the phosphate in the AS could readily be released from it, which was mainly responsible for ineffective removal of P to low levels in mixed liquor even with very high alum dose. This study provides new insight into the behavior and fate of P in the wastewater treatment plants that use alum to enhance P removal in the final effluent.

Adsorption of Ca2+ on single layer graphene oxide.

Graphene oxide (GO) holds great promise for a broad array of applications in many fields, but also poses serious potential risks to human health and the environment. In this study, the adsorptive properties of GO toward Ca2+ and Na+ were investigated using batch adsorption experiments, zeta potential measurements, and spectroscopic analysis. When pH increased from 4 to 9, Ca2+ adsorption by GO and the zeta potential of GO increased significantly. Raman spectra suggest that Ca2+ was strongly adsorbed on the GO via -COOCa+ formation. On the other hand, Na+ was adsorbed into the electrical diffuse layer as an inert counterion to increase the diffuse layer zeta potential. While the GO suspension became unstable with increasing pH from 4 to 10 in the presence of Ca2+, it was more stable at higher pH in the NaCl solution. The findings of this research provide insights in the adsorption of Ca2+ on GO and fundamental basis for prediction of its effect on the colloidal stability of GO in the environment.