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1. Thermal air oxidation changes surface and adsorptive properties of black carbon (char/biochar)

   Feng Xiao, Alemayehu H. ( January 2018 , Science of the total environment)

   In this study, we systematically investigated the effects of thermal air oxidation on the properties of biomass-derived BC made at carbonization temperatures (HTTs) of 300–700 ˚C. BC produced by including air in the carbonization step was found to have a low surface area and underdeveloped pore structure. Substantial changes of BC were observed after post-pyrolysis thermal air oxidation (PPAO). Well-carbonized BC samples made anoxically at relatively high HTTs (600 and 700 ˚C) showed, after PPAO, significant increases in N2 BET surface area (SA) (up to 700 times), porosity (< 60 Å) (up to 95 times), and adsorptivity (up to 120 times) of neutral organic species including two triazine herbicides and one natural estrogen. Partially carbonized BC made at a lower HTT (300 or 400 ˚C) showed moderate increases in these properties after PPAO, but a large increase in the intensity of Fourier transform infrared spectroscopy bands corresponding to various oxygen-containing functional groups. Well-carbonized BC samples, on the other hand, were deficient in surface oxygen functionality even after the PPAO treatment. Adsorption of the test organic compounds on BC generally trended with BET SA when it was less than 300 m2/g, but BET SA was poorly predictive of adsorption when it was greater than 300 m2/g. Overall, our results suggest that thermal reactions between molecular oxygen and BC 1) increase surface oxygen functionality more effectively for low-HTT than for high-HTT BC samples; 2) increase SA and porosity (< 60 Å) especially for high-HTT BC samples; and 3) create new adsorption sites and/or relieve steric restriction of organic molecules to micropores, thereby enhancing the adsorptivity of BC. These results will prove useful not only for understanding the fate of environmental BC but also in devising strategies for improving the practical performance of the engineered form of BC (i.e., biochar). 

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2. Study the Use of Activated Carbon and Bone Char on the Performance of Gravity Sand-Bag Water Filter

   https://doi.org/10.3390/membranes11110868  

   Fung, Eric ; Johnson, Ken I. ; Li, Wenqi ; Borges, William ; Chi, Kai ; Sharma, Sunil K. ; Madan, Yogita ; Sharma, Priyanka R. ; Hsiao, Benjamin S. ( November 2021 , Membranes)

   In this study, granulated activated charcoal (GAC) and bio charcoal (BC) is used as a filler in P3 biosand bag filter to study their filtration performance against a range of fluoride impurities from 1–1400 mg/L. A set of experiments are done to analyze the filtration efficiency of the sandbag filter against fluoride impurities after incorporating different amounts (e.g., 0.2, 2 kg) and a combination of GAC and BC. A combination of filler GAC and BC (1 kg each) have exhibited excellent results with 100% fluoride removal efficiency against 5 mg/L fluoride impurities for an entire experimental time of 165 min. It is because of the synergetic effect of adsorption caused by the high surface area (739 m2/g) of GAC and hydroxyapatite groups in BC. The data from remediation experiments using individual GAC and BC are fitted into the Langmuir and Freundlich Isotherm Models to check their adsorption mechanism and determine GAC and BC’s maximum adsorption capacity (Qm). The remediation data for both GAC and BC have shown the better fitting to the Langmuir Isotherm Model with a high R2 value of 0.994 and 0.970, respectively, showing the excellent conformity with monolayer adsorption. While the GAC and BC have presented negative Kf values of −1.08 and −0.72, respectively, for Freundlich Model, showing the non-conformity to multilayer adsorption. The Qm values obtained from Langmuir Model for GAC is 6.23 mg/g, and for BC, it is 9.13 mg/g. The pH study on adsorption efficiency of individual GAC and BC against 5 mg/L of fluoride impurities indicates the decrease in removal efficiency with an increase in pH from 3 to 9. For example, BC has shown removal efficiency of 99.8% at pH 3 and 99.5% at pH 9, while GAC has exhibited removal efficiency of 96.1% at pH 3 and 95.9% at pH 9. Importantly, this study presents the significance of the synergetic application of GAC and BC in the filters, where GAC and BC are different in their origin, functionalities, and surface characteristics. 

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3. Efficient removal of short-chain and long-chain PFAS by cationic nanocellulose

   https://doi.org/10.1039/d3ta01851b  

   Li, Duning ; Lee, Cheng-Shiuan ; Zhang, Yi ; Das, Rasel ; Akter, Fahmida ; Venkatesan, Arjun K. ; Hsiao, Benjamin S. ( May 2023 , Journal of Materials Chemistry A)

   Although most manufacturers stopped using long-chain per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), short-chain PFASs are still widely employed. Short-chain PFASs are less known in terms of toxicity and have different adsorption behavior from long-chain PFASs. Previous studies have shown electrostatic interaction with the adsorbent to be the dominant mechanism for the removal of short-chain PFASs. In this study, we designed a high charge density cationic quaternized nanocellulose (QNC) to enhance the removal of both short- and long-chain PFASs from contaminated water. Systematic batch adsorption tests were conducted using the QNC adsorbent to compare its efficiency against PFASs with varying chain lengths and functional groups. From the kinetic study, PFBA (perfluorobutanoic acid), PFBS (perfluorobutanesulfonic acid) and PFOS showed rapid adsorption rates, which reached near equilibrium values (>95% of removal) between 1 min to 15 min, while PFOA required a relatively longer equilibration time of 2 h (it obtained 90% of removal within 15 min). According to the isotherm results, the maximum adsorption capacity ( Q m ) of the QNC adsorbent exhibited the following trend: PFOS ( Q m = 559 mg g −1 or 1.12 mmol g −1 ) > PFOA ( Q m = 405 mg g −1 or 0.98 mmol g −1 ) > PFBS ( Q m = 319 mg g −1 or 1.06 mmol g −1 ) > PFBA ( Q m = 121 mg g −1 or 0.57 mmol g −1 ). This adsorption order generally matches the hydrophobicity trend among four PFASs associated with both PFAS chain length and functional group. In competitive studies, pre-adsorbed short-chain PFASs were quickly desorbed by long-chain PFASs, suggesting that the hydrophobicity of the molecule played an important role in the adsorption process on to QNC. Finally, the developed QNC adsorbent was tested to treat PFAS-contaminated groundwater, which showed excellent removal efficiency (>95%) for long-chain PFASs (C7–C9) even at a low adsorbent dose of 32 mg L −1 . However, short-chain PFASs ( i.e. , PFBA and perfluoropentanoic acid (PFPeA)) were poorly removed by the QNC adsorbent (0% and 10% removal, respectively) due to competing constituents in the groundwater matrix. This was further confirmed by controlled experiments that revealed a drop in the performance of QNC to remove short-chain PFASs at elevated ionic strength (NaCl), but not for long-chain PFASs, likely due to charge neutralization of the anionic functional group of PFASs by inorganic cations. Overall, the QNC adsorbent featured improved PFAS adsorption capacity at almost two-fold of PFAS removal by granular activated carbons, especially for short-chain PFASs. We believe, QNC can complement the use of common treatment methods such as activated carbon or ionic exchange resin to remove a wide range of PFAS pollutants, heading towards the complete remediation of PFAS contamination. 

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4. Eu(III) and Am(III) adsorption on aluminum (hydr)oxide minerals: surface complexation modeling

   https://doi.org/10.1186/s12932-023-00081-5  

   Satpathy, Anshuman ; Hixon, Amy E. ( December 2023 , Geochemical Transactions)

   Abstract Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals—corundum (α-Al 2 O 3 ), γ-alumina (γ-Al 2 O 3 ) and gibbsite (γ-Al(OH) 3 )—and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al 2 O 3 ) and γ-alumina (γ-Al 2 O 3 ) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weak sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals. Graphical Abstract 

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5. Methanotrophic methane oxidation in new biogeochemical landfill cover system

   Rai, R. K. ; Reddy, K. R. ( January 2019 , Proc. 34th International Conference on Solid Waste Technology and Management, Annapolis, MD, USA)

   Municipal solid waste (MSW) landfills are regarded as one of the major sources of greenhouse gas (GHG) emissions across the world. In order to control these emissions, an innovative and sustainable biogeochemical cover system that consists of soil, biochar and basic oxygen furnace (BOF) slag is being developed to completely eliminate fugitive methane (CH4) and carbon dioxide (CO2) emissions from the landfills. The effectiveness of such cover systems is highly dependent on the survival and activity of methanotrophs under highly alkaline conditions induced by the presence of slag. In this study, a series of microcosm batch tests on landfill cover materials in different proportions were investigated to study the effect of cover materials on microbial CH4 oxidation in the mixed as well isolated systems. Results demonstrated negligible CH4 oxidation and substantial CO2 sequestration when the BOF slag was integrated/mixed with soil (pH~7) and biochar-amended soil (pH~11). However, layered or separated cover material conditions (biochar-amended soil overlain by slag and soil overlain by slag) demonstrated promising CH4 oxidation potential, thus concluding that extreme alkaline conditions inhibit the CH4 oxidation. Overall, this study showed that a layered system consisting of the soil or biochar-amended soil layer overlain by BOF slag layer is optimal for CH4 oxidation and subsequent CO2 sequestration. Large column experiments and field test plots are being performed to evaluate the long-term performance of the proposed geochemical cover system under dynamic environmental (moisture and temperature) conditions. 

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