ABSTRACT
The present study reports a novel hay biochar functionalized with dairy effluent for enhanced tetracycline (TC) adsorption in the aqueous phase for the first time. The enrichment of hay (i.e., alfalfa) with dairy effluent led to significant accumulation of cationic metals during biochar production. The dairy effluent-functionalized alfalfa biochar (DEAF-BC) possessed strong crystallization (i.e., CaCO3), functional groups (i.e., CO3 2-, C-O stretching), and high surface area (334 m2/g) related to TC adsorption. Therefore, DEAF-BC showed higher TC adsorption capacity (835.7 mg/g) than that of the alfalfa biochar (94.5 mg/g). The adsorption isotherm and kinetic results for the DEAF-BC were correlated with the Freundlich, pseudo-second-order, and intraparticle diffusion models for TC. For the TC adsorption onto DEAF-BC, the thermodynamic analysis implied a spontaneous and endothermic process. Possible mechanisms would include metal complexation, hydrogen bonding, van der Waals forces, and π-π interaction.
ABSTRACT
This paper evaluates the design and performance of an Aboveground Permeable Reactive Barrier (APRB) system made of polyethylene mesh bags (FlowBags) containing crushed limestone and zeolite for adsorption of orthophosphate-P (PO4-P) and ammonia-N (NH4-N) from rainfall runoff. Laboratory batch experiments, simulated runoff experiments and actual APRB implementations were performed to evaluate the performance of the APRB. Batch experiments were performed to determine adsorption efficiency of crushed zeolite and limestone as reactive materials in APRB for removal of dissolved ammonium nitrogen and orthophosphate phosphorus from aqueous solutions under controlled laboratory conditions. Adsorption efficiencies of zeolite and limestone were tested individually and in combination. Results show adsorption efficiency increases when the materials are used in combination. Effects of particle size, contact time, pH, and temperature were studied. Major emphasis was given to short contact times because the contact of rainfall runoff water under field conditions with APRBs would be approximately 5 minutes. Maximum removal of approximately 70% PO4-P and NH4-N was seen at 45 degrees C in 5 minutes within a pH range of 8-11. Optimum adsorbent concentration was 0.3 ppm with 20 g limestone and 10 g of zeolites. Simulated field experiments and actual APRB field installations showed variable results. Results from field evaluations of APRB showed mixed results from very high to negligible removal of orthophosphate-P and ammonia-N at different monitoring sites and storm events. Such variability may be due to the design of the bags, other biotic and abiotic factors and various physical factors, which are absent in the laboratory conditions. Some APRB design problems were also observed under field conditions and solutions are suggested. Overall results indicate that APRBs composed of combinations of crushed zeolite and limestone will offer an effective low maintenance and green alternative to remove dissolved nutrients from runoff and protect surface water resources from eutrophication.
