Enhanced Escherichia coli removal from stormwater with bermudagrass-derived activated biochar filtration systems.

Stormwater treatment and reuse can alleviate water pollution and scarcity while current sand filtration systems showed low treatment performance for stormwater. For enhancing E. coli removal in stormwater, this study applied the bermudagrass-derived activated biochars (BCs) in the BC-sand filtration systems for E. coli removal. Compared with the pristine BC (without activation), the FeCl3 and NaOH activations increased the BC carbon content from 68.02% to 71.60% and 81.22% while E. coli removal efficiency increased from 77.60% to 81.16% and 98.68%, respectively. In all BCs, the BC carbon content showed a highly positive correlation with E. coli removal efficiency. The FeCl3 and NaOH activations also led to the enhancement of roughness of BC surface for enhancing E. coli removal by straining (physical entrapment). The main mechanisms for E. coli removal by BC-amended sand column were found to be hydrophobic attraction and straining. Additionally, under 105-107 CFU/mL of E. coli, final E. coli concentration in NaOH activated BC (NaOH-BC) column was one order of magnitude lower than those in pristine BC and FeCl3 activated BC (Fe-BC) columns. The presence of humic acid remarkably lowered the E. coli removal efficiency from 77.60% to 45.38% in pristine BC-amended sand column while slightly lowering the E. coli removal efficiencies from 81.16% and 98.68% to 68.65% and 92.57% in Fe-BC and NaOH-BC-amended sand columns, respectively. Moreover, compared to pristine BC, the activated BCs (Fe-BC and NaOH-BC) also resulted in the lower antibiotics (tetracycline and sulfamethoxazole) concentrations in the effluents from the BC-amended sand columns. Therefore, for the first time, this study indicated NaOH-BC showed high potential for effective treatment of E. coli from stormwater by the BC-amended sand filtration system compared with pristine BC and Fe-BC.

Escherichia coli inactivation in water by sulfate radical-based oxidation process using FeCl3-activated biochar/persulfate system.

Pathogenic microbes in water present great risks to environments, water resources, and human health. In the present study, for the first time, a FeCl3-activated bermudagrass-derived biochar (FA-BC) was applied to activate persulfate (PS) for E. coli inactivation. The PS activation was ascribed to the presence of Fe0 and Fe3O4 on the surface of FA-BC, and SO4·- radicals were proved to be the main role for E. coli inactivation using FA-BC activated PS system (FA-BC/PS). Decreasing the pH (5-9) and increasing the PS concentration (50-300 mg/L), reaction temperature (20-50 °C), and FA-BC dosage (100-500 mg/L) resulted in the enhancement of disinfection efficiency of E. coli using FA-BC/PS. 6.21 log reductions of E. coli were achieved within 20 min under the optimal conditions (500 mg/L FA-BC, 200 mg/L PS, pH 7, and 20 °C with 107 CFU/mL E. coli in DI water). The FA-BC/PS effectively eliminated various initial concentrations of E. coli (105-108 CFU/mL). The E. coli inactivation rate decreased from 0.1426 min-1 to 0.0883, 0.1268 min-1, and 0.1093 min-1 with the presence of 10 mg/L humic acid, 100 mg/L Cl-, and 100 mg/L HCO3-, respectively. In addition, after three cycles of disinfection tests using FA-BC/PS, the E. coli inactivation rate only slightly decreased from 0.1426 to 0.1288 min-1. The FA-BC/PS also effectively removed the E. coli in real stormwater with a 99.2 % inactivation efficiency within 180 min. The FA-BC/PS in fixed-bed column tests revealed the continuous and high inactivation of E. coli in water. Increasing the FA-BC amount (1.5 %-5 %) and PS concentration (50-200 mg/L) and decreasing the flow rate (2-4 mL/min) caused the lower E. coli concentration in effluent. Therefore, the FA-BC/PS can be considered as a promising and efficient technique for water disinfection.

FeCl3-activated biochar catalyst for heterogeneous Fenton oxidation of antibiotic sulfamethoxazole in water.

One-step FeCl3-mediated pyrolysis/activation was developed for preparation of bermudagrass (BG)-derived FeCl3-activated biochars (FA-BCs) from bermudagrass (BG) as a heterogenous Fenton catalyst for heterogeneous Fenton oxidation of sulfamethoxazole (SMX) in water. The FA-BC prepared at the FeCl3 to BG mass ratio of 2 (FA-BC) exhibited higher adsorption and Fenton oxidation of SMX than other mass ratios of the FeCl3 to BG. FA-BC presented the great surface area (835 m2/g) and high SMX adsorption capacity (195 mg SMX/g BC), which was higher than various BCs in the previous studies. Additionally, the surface of FA-BC was attached with Fe2O3, Fe0, and Fe3O4 after the FeCl3 activation. Under the optimal conditions for Fenton reaction (SMX concentration, 100 mg/L; loading of FA-BC, 0.1 g/L; dose of H2O2, 200 mg/L; temperature, 20 °C; pH 3; reaction time, 12 h), SMX and COD removal efficiencies reached 99.94% and 65.19%, respectively. Increasing reaction temperature from 20 to 50 °C significantly improved the SMX oxidation rate from 0.46 to 1.04 h-1. The HO· radicals were proved to play a major role during the Fenton oxidation of SMX. In addition, the SMX solution treated by Fenton oxidation showed much less toxicity than the initial SMX solution. Additionally, the reusability tests of FA-BC indicated that 89.58% removal efficiency for SMX was still achieved after 3 cycles of Fenton oxidation under the optimal conditions. Furthermore, FA-BC can also efficiently remove SMX from the dairy wastewater. Therefore, FA-BC showed a high potential to eliminate aqueous SMX through adsorption and heterogeneous Fenton oxidation.

Sustainable use of Ca(OH)2 modified biochar for phosphorus recovery and tetracycline removal from water.

To prevent possible secondary pollution from phosphorus-loaded biochar (BC) in agricultural systems, this study investigated the sustainable use of Ca(OH)2 modified wood biochars (Ca-BCs) for P recovery while significantly lowering the tetracycline (TC) adsorption onto Ca-BCs. Ca-BCs were prepared via calcination of mixtures of Ca(OH)2 and wood BC under 100-500 °C for removing P and TC from water. Compared to the pristine BC (without Ca(OH)2 modification), Ca-BC100 (Ca-BC prepared at 100 °C) showed a significant increase of P adsorption capacity from 4.00 to 138.70 mg/g due to reactive interaction between P and Ca(OH)2 on Ca-BC while decrease of TC adsorption capacity from 62.17 to 20.86 mg/g owing to decrease of surface area from 260.50 to 120.26 m2/g. Batch adsorption tests implied that the P adsorption on Ca-BC100 would occur mainly via electrostatic attraction (pH > 2.1) and formation of hydroxylapatite (Ca5(PO4)3(OH)) between phosphate and Ca(OH)2. In addition, Ca-BC100 reacted with TC via electrostatic attraction (pH > 7.6), complexation, hydrogen bond, and π-π interactions. P and TC adsorption onto Ca-BC100 was a chemical, endothermic, and spontaneous process. The dynamic adsorption experiments using a fixed bed column filled with Ca-BC100 indicated that Ca-BC100 could continuously and effectively remove P and TC from water. Ca-BC100 also effectively lowered P and COD in the dairy wastewater. Under the environmentally relevant conditions, continuous treatment of water containing P and TC using the pristine BC followed by Ca-BC100 showed the pristine BC removed 96% of TC and only 6% of P from water while Ca-BC100 made high recovery of P (94% of P) with negligible TC. Therefore, Ca-BC100 could be used for effective recovery of P with negligible TC from wastewater, and then applied to agricultural systems as a sustainable and safe P-rich biofertilizer.

Thermally enhanced adsorption and persulfate oxidation-driven regeneration on FeCl3-activated biochar for removal of microcystin-LR in water.

In this study, a cyclic process of adsorption and persulfate (PS) oxidation-driven regeneration using FeCl3-activated biochar (FA-BC) was suggested as a novel remediation process to remove microcystin-LR (MC-LR) from water. For enhancing overall treatment efficiency and cost effectiveness, the impacts of temperature on adsorption and PS oxidation-driven regeneration were investigated. The increase of temperature resulted in the increase of MC-LR adsorption rate on FA-BC due to the enhanced MC-LR diffusivity in water. Moreover, the MC-LR oxidation and PS reaction rates during the PS regeneration on FA-BC were remarkably improved by factors of 3.4 and 3.5 with increasing temperature from 20 °C to 50 °C. Both diffusion and desorption of MC-LR from FA-BC were thought to be the key factors for controlling the MC-LR oxidation rate during the PS regeneration of MC-LR. In addition, the decrease of pH (from 10 to 4) and increase of PS concentration (from 100 to 400 mg/L) enhanced the regeneration efficiency for MC-LR-spent FA-BC. The four cycles of adsorption-PS regeneration (200 mg/L PS, pH 6, and 50 °C) resulted in 92.81% regeneration efficiency in DI water and 82.89% in lake water. However, the four cycles of adsorption-PS regeneration led to the reduction of surface area (from 835 to 413 m2/g), oxidation of carbon surface and slight reduction of Fe0 on FA-BC. In overall, the cyclic adsorption-PS regeneration at higher temperature could provide practical reuse of FA-BC for cost-effective treatment of aqueous MC-LR.

Effects of Mechanical Refining on Anaerobic Digestion of Dairy Manure.

Mechanical refining (MR) is a cost-effective pretreatment in biochemical conversion processes that is employed to overcome biomass recalcitrance. This work studied the effects of MR on biogas and methane produced by the anaerobic digestion (AD) of dairy manure. The cumulative gas volume and yield from the AD of manure refined at 6k revolutions increased by 33.7 and 7.7% for methane and by 32.0 and 6.4% for biogas, respectively, compared to the unrefined manure. This enhancement was reached by increasing manure solubilization, reducing particle size, and achieving external fibrillation and internal delamination of fibers in manure. However, the highly refined manure (subjected to 60k revolutions) exhibited methane and biogas yields that were reduced by 9.5 and 1.5%, respectively. This decrease was observed because the pore structure was ruptured, and finely ground manure particles were aggregated together at high revolutions (60k), thereby inhibiting the release of organic matter from the manure. Therefore, this study indicates that the MR for pretreatment of dairy manure could have great potential for significantly enhancing AD of dairy manure. Further studies will include optimization of conditions of mechanical refining (i.e., mechanical intensity, process time), a continuous AD of dairy manure pretreated by the MR, and scale-up with cost evaluation.

Adsorption and regeneration on iron-activated biochar for removal of microcystin-LR.

Novel iron activated biochars (FA-BCs) were prepared via simultaneous pyrolysis and activation of FeCl3-pretreated bermudagrass (BG) for removing microcystin-LR (MC-LR) in aqueous solution. Compared to the raw BC (without activation), the surface area and adsorption capacity of FA-BC at iron impregnation ratio of 2 (2 g FeCl3/g BG) were enhanced from 86 m2/g and 0.76 mg/g to 835 m2/g and 9.00 mg/g. Moreover, FA-BC possessed various iron oxides at its surface which provided the catalytic capacity for regeneration of MC-LR spent FA-BC and magnetic separation after the MC-LR adsorption. Possible mechanisms for the MC-LR adsorption onto FA-BC would include electrostatic attraction, π+-π, hydrogen bond, and hydrophobic interactions. The detailed adsorption studies indicated mainly chemisorption and intra-particle diffusion limitation would participate in the adsorption process. The thermal regeneration at 300 °C kept high regeneration efficiency (99-100%) for the MC-LR spent FA-BC during four cycles of adsorption-regeneration. In addition, the high regeneration efficiency (close to 100%) was also achieved by persulfate oxidation-driven regeneration. FA-BC also exhibited high adsorption capacity for the MC-LR from the real lake water to meet the MC-LR concentration below 1 µg/L as a safe guideline suggested by WHO.

Iron-activated bermudagrass-derived biochar for adsorption of aqueous sulfamethoxazole: Effects of iron impregnation ratio on biochar properties, adsorption, and regeneration.

This work focused on the impacts of FeCl3 impregnation ratio on the properties of FeCl3-activated bermudagrass (BG)-derived biochars (IA-BCs), adsorption of sulfamethoxazole (SMX) onto IA-BCs and regeneration of SMX-spent IA-BC. Compared with the control BC (85.82 m2/g), IA-BCs made via pyrolysis with FeCl3 to BG mass ratio between 1 and 3 (1-3 g FeCl3/g BG) resulted in significantly enhancing surface area (1014-1035 m2/g), hydrophobicity, Fe content in IA-BCs (3.87-7.27%), and graphitized carbon. The properties of IA-BCs supported magnetic separation and higher adsorption (32-265 mg SMX/g BC) than the control BC (6-14 mg SMX/g BC) at various pH. Adsorption experiments indicated various adsorption mechanisms between SMX and IA-BCs via π-π EDA, hydrophobic interactions, and hydrogen bond with intraparticle diffusion limitation. The adsorption was also found to be spontaneous and exothermic. The IA-BC made at FeCl3 to BG mass ratio of 2 (IA-BC2.0) showed the maximum adsorption capacity for SMX (253 mg SMX/g BC) calculated from Langmuir isotherm model. Additionally, both NaOH desorption and thermal oxidation showed effective regeneration of SMX-saturated IA-BC2.0 over multiple cycles. After three cycles of adsorption-regeneration, 64% and 62% of regeneration efficiencies were still achieved under thermal treatment at 300 °C and desorption with 0.1 M NaOH solution, respectively, indicating a cost-efficient adsorbent for the elimination of SMX in water.

Chemical Activation of Forage Grass-Derived Biochar for Treatment of Aqueous Antibiotic Sulfamethoxazole.

Chemically activated forage Bermudagrass-derived biochar (A-BC) was produced, characterized, and utilized for adsorption of sulfamethoxazole (SMX) in water for the first time. After NaOH activation, A-BC showed a higher surface area (1991.59 m2/g) and maximum adsorption capacity for SMX (425 mg SMX/g BC) than those of various biochars and commercial activated carbons. The detailed analysis for adsorption of SMX onto A-BC indicated the efficient sorption of SMX through π-π EDA and hydrophobic and hydrogen bond interactions. Additionally, the adsorption of SMX on A-BC was limited by pore and liquid film diffusions. The SMX adsorption on A-BC was found to be endothermic and spontaneous from thermodynamic studies. Furthermore, the highly efficient regeneration of SMX-saturated A-BC over multiple cycles was achieved by NaOH-driven desorption, indicating that the adsorption of SMX onto A-BC would have high potential for cost-effective solution for elimination of SMX from water.

Expression of a thermotolerant laccase from Pycnoporus sanguineus in Trichoderma reesei and its application in the degradation of bisphenol A.

The laccase gene from Pycnoporus sanguineus was cloned and inserted between the strong Pcbh1 promoter and the Tcbh1 terminator from Trichoderma reesei to form the recombinant plasmid pCH-lac. Using Agrobacterium-mediated technique, the pCH-lac was integrated into the chromosomes of T. reesei. Twenty positive transformants were obtained by employing hygromycin B as a selective agent. PCR was used to confirm that the laccase gene was integrated into the chromosomal DNA of T. reesei. Laccase production by recombinant transformants was performed in shaking flasks, and the activity of laccase reached 8.8 IU/mL after 96-h fermentation under a batch process, and 17.7 IU/mL after 144-h fermentation using a fed-batch process. SDS-PAGE analysis of the fermentation broth showed that the molecular mass of the protein was about 68 kDa, almost the same as that of the laccase produced by P. sanguineus, which indicated that laccase was successfully expressed in T. reesei and secreted out of the cells. The laccase produced by the recombinant T. reesei showed good thermal stability, and could degrade the toxic phenolic material bisphenol A efficiently, after 1-h reaction with 0.06 IU/mL laccase and 0.5 mmol/L ABTS as the mediator at 60 °C and pH 4.5, the degradation rate reached 95%, which demonstrated that it had great potential value in treating the household garbage and wastewater containing the bisphenol A.

Simultaneous production of laccase and degradation of bisphenol A with Trametes versicolor cultivated on agricultural wastes.

Solid state fermentation with Trametes versicolor was carried out on agricultural wastes containing bisphenol A (BPA). It was found that BPA degradation was along with the occurrence of laccase production, and wheat bran and corn straw were identified as suitable mixed substrates for laccase production. In the process of BPA degradation with T. versicolor, laccase activity increased rapidly at the 6th-10th day after inoculation. Moreover, BPA can enhance the production of laccase. After 10 days of fermentation, degradation rate of BPA exceeded 90% without the usage of mediators ABTS and acetosyringone at pH 4.0-8.0. In addition, metal ions did not affect the BPA degradation with T. versicolor. In vitro, the optimum pH range of BPA degradation with laccase was in the acidic region with the optimal performance of pH 5.0. Metal ions Cu2+, Zn2+, and Co2+ showed little effect on BPA degradation. However, Fe3+ and Fe2+ substantially inhibited the BPA degradation. Natural mediator acetosyringone showed optimum enhancement on BPA degradation. Greater than 90% of the estrogenic activity of BPA was removed by T. versicolor and its laccase. Compared to in vitro degradation with laccase, this study shows that the process of simultaneous laccase production and BPA degradation with T. versicolor was more advantageous since BPA can enhance the laccase production, mediators were unnecessary, degradation rate was not affected by metal ions, and the applicable pH range was broader. This study concludes that T. versicolor and laccase have great potential to treat industrial wastewater containing BPA.

Poly-γ-glutamic acid produced from Bacillus licheniformis CGMCC 2876 as a potential substitute for polyacrylamide in the sugarcane industry.

As an environmentally friendly and industrially useful biopolymer, poly-γ-glutamic acid (γ-PGA) from Bacillus licheniformis CGMCC 2876 was characterized by the high-resolution mass spectrometry and (1)H NMR. A flocculating activity of 11,474.47 U mL(-1) obtained with γ-PGA, and the effects of carbon sources, ions, and chemical properties (D-/L-composition and molecular weight) on the production and flocculating activity of γ-PGA were discussed. Being a bioflocculant in the sugar refinery process, the color and turbidity of the sugarcane juice was IU 1,877.36 and IU 341.41 with 0.8 ppm of γ-PGA, respectively, which was as good as the most widely used chemically synthesized flocculant in the sugarcane industry--polyacrylamide with 1 ppm. The γ-PGA produced from B. licheniformis CGMCC 2876 could be a promising alternate of chemically synthesized flocculants in the sugarcane industry.