Definitive Review of Nanobiochar.

Nanobiochar is an advanced nanosized biochar with enhanced properties and wide applicability for a variety of modern-day applications. Nanobiochar can be developed easily from bulk biochar through top-down approaches including ball-milling, centrifugation, sonication, and hydrothermal synthesis. Nanobiochar can also be modified or engineered to obtain "engineered nanobiochar" or biochar nanocomposites with enhanced properties and applications. Nanobiochar provides many fold enhancements in surface area (0.4-97-times), pore size (0.1-5.3-times), total pore volume (0.5-48.5-times), and surface functionalities over bulk biochars. These enhancements have given increased contaminant sorption in both aqueous and soil media. Further, nanobiochar has also shown catalytic properties and applications in sensors, additive/fillers, targeted drug delivery, enzyme immobilization, polymer production, etc. The advantages and disadvantages of nanobiochar over bulk biochar are summarized herein, in detail. The processes and mechanisms involved in nanobiochar synthesis and contaminants sorption over nanobiochar are summarized. Finally, future directions and recommendations are suggested.

Contribution of modified P-enriched biochar on pH buffering capacity of acidic soil.

Biochar can directly hold cations in soil because of the negative charge that exists on its surfaces. Besides, improving soil cation exchange capacity, the negative charges on biochar surfaces can buffer acid soil by protonation and deprotonation mechanisms. Moreover, biochar ameliorates soil acidity due to the presence of oxides, carbonates, and hydroxides of its basic cations (Ca, Na, K, and Mg). Both biochar surface functional group and basic cation concentrations can be altered by modification with chemical agents which can affect its soil pH buffering capacity. However, the impact of modified biochar application on soil pH buffering capacity is still scanty. This study investigated the pH buffering capacity of acidic soil amended with three P-enriched modified Douglas fir biochars and compared this buffering capacity to amendment with untreated Douglas fir biochar. These three P-enriched biochars, were prepared by treating Douglas fir biochar (DFB), respectively, with: 1) anhydrous calcium chloride (CaCl2) and potassium phosphate monobasic (KH2PO4), 2) calcium carbonate (CaCO3) and diammonium phosphate {(NH4)2HPO4} and 3) an aqueous solution of magnesium sulfate (MgSO4), potassium hydroxide (KOH) and potassium phosphate monobasic (KH2PO4). The three P-enriched biochars were designated as CCPP, CAPP and MSPP, respectively. The soil pH buffering abilities were largely dependent on the added biochar's alkalinity and ash contents. The residual soil CEC was highly correlated (r ≥ 0.9), with the soil buffering capacity. Both alkalinity and pH buffering capacity improved following the order CCAP > CCPP > MSPP > DFB, while residual soil CEC followed the order CAPP > MSPP > CCPP > DFB. The pH buffering capacity of the soil after amendments with 10% CAPP, CCPP MSPP and BFB rose by 84.8, 58.3, 3.0 and 2.5%, respectively. Whereas MSPP had higher concentrations of K+ and Mg2+, greater concentrations of Ca2+ were present in CCAP and CCPP than MSPP. So, Ca2+ concentrations in biochar exerts a greater influence on alkalinity and buffering capacity than Mg2+ and K+ because of 1) its smaller effective hydration radius and larger charge density. 2) calcium hydroxide has a greater water solubility than magnesium hydroxide providing more available base. Since pH buffering capacity depends on cation exchange sites, soil additives containing Ca2+ are prone to create greater impacts than Mg2+ and K+ additives.

Teaching Old Polymers New Tricks: Improved Synthesis and Anomalous Crystallinity for a Lost Semi-Fluorinated Polyaryl Ether via Interfacial Polymerization of Hexafluoroacetone Hydrate and Diphenyl Ether.

A practical and direct electrophilic polymerization of hexafluoroacetone hydrate with diphenyl ether toward the preparation of semi-fluorinated polyaryl ethers (PAE) is reported. Electrophilic aromatic substitution (EAS) polymerization under interfacial conditions with phase transfer catalyst (Aliquat 336) proceeds in trifluoromethanesulfonic anhydride by generation of trifluoromethanesulfonic acid and the protonated hexafluoroacetone (HFA) in situ affording 1,1,1,3,3,3-hexafluoroisopropylidene (6F) PAE with high regioselectivity (4,4'-DPE) and high molecular weight (≈60 kDa). Although first reported in a 1966 US Patent by DuPont using harsh conditions, improved synthetic methods or modern characterization has not been disclosed until now. Despite the presence of the 6F group, known to impart disordered morphology, this simple semi-fluorinated PAE exhibits anomalous crystallinity with polymorphic melting points (Tm ) ranging from 230-309 °C, high solubility in common organic solvents, a glass transition (Tg ) of 163 °C, and thermo-oxidative stability above 500 °C. Tough optically clear films prepared from solution give transmittance higher than 90% throughout the visible region. Synthesis, mechanistic aspects, and characterization including surface and dielectric properties are discussed.

Efficient aqueous molybdenum removal using commercial Douglas fir biochar and its iron oxide hybrids.

Molybdenum (Mo) is a naturally-occurring trace element in drinking water. Most commonly, molybdate anions (MoO42-) are in well water and breast milk. In addition, it is used in medical image testing. Recently, the EPA classified Mo as a potential contaminant, as exposure can lead to health effects such as gout, hyperuricemia, and even lung cancer. We have assessed the sorptive removal of aqueous molybdate using Douglas fir biochar (DFBC) and a hybrid DFBC/Fe3O4 composite containing chemically-coprecipitated iron oxide (Fe3O4). Adsorption was studied at various: pH values, equilibrium times (5 min-24 h), initial Mo concentrations (2.5-1000 mg/L), and temperatures (5, 25, and 40 °C) using batch sorption and fixed-bed column equilibrium methods. Langmuir capacities for DFBC and DFBC/Fe3O4 (at pH 3, 2 hrs equilibrium) were within 459.3-487.9 mg/g and 288-572 mg/g, respectively. These adsorbents and their Mo-laden counterparts were characterized by elemental analysis, BET, PZC, SEM, TEM, EDS, XRD, and XPS. MoO42- adsorption on DFBC is thought to be governed primarily via electrostatic attraction. Adsorption by DFBC/Fe3O4 is primarily governed by chemisorption onto magnetite surface hydroxyl groups, while electrostatics prevail in the DFBC-exposed phase. Stoichiometric precipitation of iron molybdates triggered by iron dissolution was also considered. The data suggest that DFBC and DFBC/Fe3O4 are promising candidates for molybdate sorption.

Batch and fixed bed sorption of low to moderate concentrations of aqueous per- and poly-fluoroalkyl substances (PFAS) on Douglas fir biochar and its Fe3O4 hybrids.

Per- and poly-fluoroalkyl substances (PFAS) can cause deleterious effects at low concentrations (70 ng/L). Their remediation is challenging. Aqueous µg/L levels of PFOS, PFOS, PFOSA, PFBS, GenX, PFHxS, PFPeA, PFHxA, and PFHpA (abbreviations defined in Table 1) multi-component adsorption (pH dependence, kinetics, isotherms, fixed-bed adsorption, regeneration, complex matrix) was studied on commercial Douglas fir biochar (BC) and its Fe3O4-containing BC. BC is a waste product when syn-gas is produced in a large scale from wet Douglas fir wood fed to gasification at 900-1000 °C and held for 1-20 s. This generates a relatively high surface area (∼700 m2/g) and large pore volume (∼0.25 cm3/g) biochar. Treatment of BC with FeCl3/FeSO4 and NaOH to chemically precipitate Fe3O4 onto BC. BC and its magnetic Fe3O4/BC analogue rapidly adsorbed (20-45 min equilibrium time) significant amounts of PFOS (∼14.6 mg/g) and PFOA (∼652 mg/g) at natural waters' pH range (6-8). Adsorption from µg/L concentrations has produced remediated aqueous PFAS concentrations of ∼50 ng/L or below the detection limits, which is closing in on EPA advisory limits. Column capacities of PFOS were 215.3 mg/g on BC and 51.9 mg/g Fe3O4/BC vs 53.0 mg/g and 21.8 mg/g, respectively, for PFOA. Hydrophobic and electrostatic interactions are thought to drive this sorption. Successful stripping regeneration by methanol was achieved. Thus, hydrophobic Douglas fir biochar produced by fast high temperature pyrolysis and its Fe3O4/BC analogue are adsorbent candidates for PFAS remediation from the dilute PFAS concentrations often found in polluted environments. Small Fe3O4/BC particles can be magnetically removed from batch treatments avoiding filtration.

Pseudo-resonance structures in chiral alcohols and amines and their possible aggregation states.

We now report that some chiral compounds, like alcohols, which are not sterically hindered atropisomers nor epimer mixtures, exhibit two sets of simultaneous NMR spectra in CDCl3. Some other chiral alcohols also simultaneously exhibit two different NMR spectra in the solid state because two different conformers, A and B had different sizes because their corresponding bond lengths and angles are different. These structures were confirmed in the same solid state by X-ray. We designate these as pseudo-resonance for a compound exhibiting several different corresponding lengths that simultaneously coexist in the solid state or liquid state. Variable-temperature NMR, 2D NMR methods, X-ray, neutron diffraction, IR, photo-luminesce (PL) and other methods were explored to study whether new aggregation states caused these heretofore unknown pseudo-resonance structures. Finally, eleven chiral alcohols or diols were found to co-exist in pseudo-resonance structures by X-ray crystallography in a search of the CDS database.

Iron/titanium oxide-biochar (Fe2TiO5/BC): A versatile adsorbent/photocatalyst for aqueous Cr(VI), Pb2+, F- and methylene blue.

This is the first report of the metal Fe-Ti oxide/biochar (Fe2TiO5/BC) composite for simultaneous removal of aqueous Pb2+, Cr6+, F- and methylene blue (MB). Primary Fe2TiO5 nano particles and aggregates were dispersed on a high surface area Douglas fir BC (∼700 m2/g) by a simple chemical co-precipitation method using FeCl3 and TiO(acac)2 salts treated by base and heated to 80 °C. This was followed by calcination at 500 °C. This method previously was used without BC to make the neat mixed oxide Fe2TiO5, exhibiting a lower energy band gap than TiO2. Adsorption of Cr(VI), Pb(II), fluoride, and MB on Fe2TiO5/BC was studied as a function of pH, equilibrium time, initial adsorbate concentration, and temperature. Adsorption isotherm studies were conducted at 5, 25, and 45 ℃ and kinetics for all four adsorbates followed the pseudo second order model. Maximum Langmuir adsorption capacities for Pb2+, Cr6+, F- and MB at their initial pH values were 141 (pH 2), 200 (pH 5), 36 (pH 6) and 229 (pH 6) mg/g at 45 ℃ and 114, 180, 26 and 210 mg/g at 25 ℃, respectively. MB was removed from the water on Fe2TiO5/BC by synergistic adsorption and photocatalytic degradation at pH 3 and 6 under UV (365 nm) light irradiation. Cr6+, Pb2+, F-, and MB each exhibited excellent removal capacities in the presence of eight different competitive ions in simulated water samples. The removal mechanisms on Fe2TiO5/BC and various competitive ion interactions were proposed. Some iron ion leaching at pH 3 catalyzed Photo-Fenton destruction of MB. Fe2TiO5, BC, and Fe2TiO5/BC bandgaps were studied to help understand photocatalysis of MB and to advance supported metal oxide photodegradation using smaller energy band gaps than the larger bandgap of TiO2 for water treatment. A long range goal is to photocatalytically destroy some sorbates with adsorbents to avoid the need for regeneration steps.

Lead immobilization in simulated polluted soil by Douglas fir biochar-supported phosphate.

This study compared the lead (Pb2+) immobilization efficacy of biochar-supported phosphate to conventional in-situ heavy metal immobilization methods (with lime, neat biochar and phosphate). The biochar-supported phosphate was obtained by treating Douglas fir biochar (BC) with anhydrous calcium chloride and potassium dihydrogen phosphate. The amount of Pb2+ immobilized was determined by comparing the concentration of ammonium nitrate extractable Pb2+ lead from lead-spiked soil (without amendment) to that of a 30 d incubation with (a) lead-spiked soil plus 5% (wt./wt.) biochar supported-phosphate, (b) lead-spiked soil plus 5% (wt./wt.) untreated Douglas fir biochar, (c) lead-spiked soil plus 5% (w/w) lime and (d) lead-spiked soil plus 5% (wt./wt.) potassium dihydrogen phosphate. The control (lead-spiked soil without amendment) produced the largest quantity (96.08 ± 9.22 mg L-1) of NH4NO3-extractable Pb2+, while lead-spiked soil treated with 5% (wt./wt.) biochar-supported phosphate resulted in the lowest quantity of NH4NO3 extractable Pb2+ (0.3 ± 0.2 mg L-1). The mechanism for immobilization of Pb2+ by BP occurs at pH < 7 through dissolution of hydroxyapatite embedded in BP during modification, followed by precipitation of insoluble Pb10(PO4)6(OH)2. The residual lead fraction in the lead-spiked soil increased by 20.9% following amendment with BP. These results indicate that biochar-supported phosphate is a candidate to reduce lead mobility (bioavailability) in polluted soil. This amendment may lower Pb2+ uptake into plants while minimizing the potential for water contamination due to Pb2+mobility.

Biochar-supported polyaniline hybrid for aqueous chromium and nitrate adsorption.

Biochar adsorbents can remove environmental pollutants and the remediation of Cr(VI) and nitrate are considered. Cr(VI) is a proven carcinogen causing serious health issues in humans and nitrate induced eutrophication causes negative effect on aquatic systems around the world. Douglas fir biochar (DFBC), synthesized by fast pyrolysis during syn gas production, was treated with aniline. Then, a polyaniline biochar (PANIBC) composite containing 47 wt% PANI was prepared by precipitating PANI on DFBC surfaces by oxidative chemical polymerization of aniline in 2M HCl. PANIBC exhibited a point of zero charge (PZC) of 3.0 and 8.2 m2/g BET (N2) surface area. This modified biochar was characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM) morphology and surface elements, and oxidation states by X-ray photoelectron spectroscopy (XPS). PANIBC exhibited positive surface charge below pH 3, making it an outstanding adsorbent, for Cr(VI) removal. Cr(VI) and nitrate removal mechanisms are presented based on XPS analysis. DFBC and PANIBC Cr(VI) and nitrate adsorption data were fitted to Langmuir and Freundlich isotherm models with maximum Langmuir adsorption capacities of 150 mg/g and 72 mg/g, respectively. Cr(VI) and nitrate removal at pH 2 and 6 were evaluated by reducing the amount of PANI (9 wt%) dispersed on to DFBC. Adsorption capacities verses temperature studies revealed that both Cr(VI) and nitrate adsorption are endothermic and thermodynamically favored. Regeneration studies were conducted on both DFBC and PANIBC using 0.1M NaOH and PANIBC exhibited excellent sorption capacities for Cr(VI) and nitrate in lake water samples and in the presence of competitive ions.

Ciprofloxacin and acetaminophen sorption onto banana peel biochars: Environmental and process parameter influences.

Environmental (pH, temperature ionic strength, cations, anions) and process (pyrolysis temperature, particle size, adsorbent dosage, initial concentration) parameters were evaluated for ciprofloxacin and acetaminophen sorption onto a series of sustainable banana peel biochars. Ciprofloxacin and acetaminophen were chosen as model pharmaceuticals for removal owing to their worldwide presence in aquatic systems. After pyrolytic preparation from 450 to 750 °C, the biochars were qualitatively and quantitatively characterized by physicochemical, morphological, mineralogical and elemental analyses. Batch sorption studies were employed to evaluate the pH effects from 2 to 10, biochar pyrolysis temperatures (450, 550, 650, and 750 °C), particle sizes (30-50, 50-100, 100-150 BSS mesh), adsorbent dosages (0.5, 1.0, 2.0 g/L), adsorbate concentrations (0.5-200 ppm) and uptake temperatures (10, 25, 40 °C) on sorption efficiency. Maximum pharmaceutical sorption is achieved by the biochar prepared at 750 °C. Sorption rate increased with decrease in biochar particle size from 30 to 50 to 100-150 BSS mesh. Relationships between biochar properties and their sorptive potential showed positive correlations with surface area, total pore volume, %C, %ash and C/N molar ratios. Sorption data was modelled using different isotherm models and both kinetic and thermodynamic equations. Maximum Langmuir capacities of ciprofloxacin and acetaminophen on BPBC750 were 23.3 and 40.8 mg/g at 10 °C; 21.0 and 49.93 mg/g at 25 °C and 20.42 and 57.3 mg/g at 45 °C, respectively. Langmuir isotherm fittings and thermodynamic parameters confirmed the exothermic sorption (for ciprofloxacin) and endothermic sorption (for acetaminophen). The role of ionic strength, cations and anions on pharmaceuticals sorption were evaluated. H-bonding, π-π-interactions and pore diffusion were major contributors to pharmaceutical sorption.

Lignite, thermally-modified and Ca/Mg-modified lignite for phosphate remediation.

Aqueous phosphate uptake is needed to reduce global eutrophication. Negatively charged adsorbent surfaces usually give poor phosphate sorption. Chemically- and thermally-modified lignite (CTL) was prepared by impregnating low-cost lignite (RL) with Ca2+ and Mg2+ cations, basified with KOH (pH Ì´ 13.9), followed by a 1 h 600 °C pyrolysis under nitrogen. CTL has a positive surface (PZC = 13) due to basic surface Ca and Mg compounds, facilitating the aqueous phosphate uptake. CaCO3, MgO, Ca(OH)2, and Mg(OH)2 surface phases with 0.22 µm particle sizes were verified by XRD, XPS, SEM, TEM, and EDX before and after phosphate uptake. Higher amounts of these mineral phases promoted more CTL phosphate uptake than raw lignite (RL) and thermally treated lignite (TL) without Ca/Mg modification. Phosphorous uptake by Ca2+/Mg2+ occurs not by classic adsorption but by stochiometric precipitation of Mg3(PO4)2, MgHPO4, Ca3(PO4)2, and CaHPO4. This offers the potential of substantial uptake capacities. CTL's phosphate removal is pH-dependent; the optimum pH was 2.2. Water-washed CTL exhibited a maximum Langmuir phosphate uptake capacity of 15.5 mg/g at pH 7, 6 and 14 times higher than that of TL and RL, respectively (particle size <150 µm, adsorbent dose 50 mg, 25 mL of 25-1000 ppm phosphate concentration, 24 h, 25 °C). The unwashed CTL exhibited a maximum Langmuir phosphate removal capacity (80.6 mg/g), 5.2-times greater than the washed CTL (15.5 mg/g). Insoluble Ca2+ and Mg2+ phosphates/hydrophosphate particles dominated CTL's phosphate removal. Phosphates were recovered from both exhausted unwashed and washed CTL better in HCl than in NaOH. P-laden washed CTL exhibited a slow phosphate leaching rate under initial pH of 6.5-7.5 (52-57% over 20 days) after phosphate uptake, indicating it could serve as a slow-release fertilizer. Unwashed CTL retained more phosphates than washed CTL (cumulative qe for 4 cycles = 391.8 mg/g vs 374.7 mg/g) and potentially improves soil fertility more.

High capacity aqueous phosphate reclamation using Fe/Mg-layered double hydroxide (LDH) dispersed on biochar.

Phosphate is a primary plant nutrient, serving integral role in environmental stability. Excessive phosphate in water causes eutrophication; hence, phosphate ions need to be harvested from soil nutrient levels and water and used efficiently. Fe-Mg (1:2) layered double hydroxides (LDH) were chemically co-precipitated and widely dispersed on a cheap, commercial Douglas fir biochar (695 m2/g surface area and 0.26 cm3/g pore volume) byproduct from syn gas production. This hybrid multiphase LDH dispersed on biochar (LDHBC) robustly adsorbed (~5h equilibrium) phosphate from aqueous solutions in exceptional sorption capacities and no pH dependence between pH 1-11. High phosphate Langmuir sorption capacities were found for both LDH (154 to 241 mg/g) and LDH-modified biochar (117 to 1589 mg/g). LDHBC was able to provide excellent sorption performance in the presence of nine competitive anion contaminants (CO32-, AsO43-, SeO42-, NO3-, Cr2O72-, Cl-, F-, SO42-, and MoO42-) and also upon remediating natural eutrophic water samples. Regeneration was demonstrated by stripping with aqueous 1 M NaOH. No dramatic performance drop was observed over 3 sorption-stripping cycles for low concentrations (5 ppm). The adsorbents and phosphate-laden adsorbents were characterized using Elemental analysis, BET, PZC, TGA, DSC, XRD, SEM, TEM, and XPS. The primary sorption mechanism is ion-exchange from low to moderate concentrations (10-500 ppm). Chemisorption and stoichiometric phosphate compound formation were also considered at higher phosphate concentrations (>500 ppm) and at 40 °C. This work advances the state of the art for environmentally friendly phosphate reclamation. These phosphate-laden adsorbents also have potential to be used as a slow-release phosphate fertilizer.

Smart Adsorbents for Aquatic Environmental Remediation.

A noticeable interest and steady rise in research studies reporting the design and assessment of smart adsorbents for sequestering aqueous metal ions and xenobiotics has occurred in the last decade. This motivates compiling and reviewing the characteristics, potentials, and performances of this new adsorbent generation's metal ion and xenobiotics sequestration. Herein, stimuli-responsive adsorbents that respond to its media (as internal triggers; e.g., pH and temperature) or external triggers (e.g., magnetic field and light) are highlighted. Readers are then introduced to selective adsorbents that selectively capture materials of interest. This is followed by a discussion of self-healing and self-cleaning adsorbents. Finally, the review ends with research gaps in material designs.

KOH-activated high surface area Douglas Fir biochar for adsorbing aqueous Cr(VI), Pb(II) and Cd(II).

Biochar has become a popular research topic in sustainable chemistry for use both in agriculture and pollution abatement. To enhance aqueous Cr(VI), Pb(II) and Cd(II) removal efficiency, high surface area (535 m2/g) byproduct Douglas fir biochar (DFBC) from commercial syn-gas production obtained by fast pyrolysis (900-1000 °C, 1-10 s), was subjected to a KOH activation. KOH-activated biochar (KOHBC) underwent a remarkable surface area increase to 1049 m2/g and a three-fold increase in pore volume (BET analysis). Batch sorption studies on KOHBC verses pH revealed that the highest chromium, lead and cadmium removal capacities occurred at pH 2.0, 5.0 and 6.0, respectively. KOHBC exhibited much higher adsorption capacities than unactivated DFBC. Heavy metal loadings onto KOHBC were characterized by scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Sorption of Cr(VI), Pb(II) and Cd(II) all followed pseudo-second order kinetics and the Langmuir adsorption model. The highest Langmuir adsorption capacities at the respective pH's of maximum adsorption were 140.0 mg g-1 Pb(II), 127.2 mg g-1 Cr(VI) and 29.0 mg g-1 Cd(II). Metal ions spiked into natural and laboratory waste water systems exhibited high sorption capacities. Desorption studies carried out using 0.1 M HCl revealed that Pb(II) adsorption onto the KOHBC surface is reversible. Portions of Cd(II) and Cr(VI) adsorbed strongly onto KOHBC were unable to be desorbed by 0.1 M HCl and 0.1 M NaOH.

Coronavirus (SARS-CoV-2) in the environment: Occurrence, persistence, analysis in aquatic systems and possible management.

The year 2020 brought the news of the emergence of a new respiratory disease (COVID-19) from Wuhan, China. The disease is now a global pandemic and is caused by a virus named SARS-CoV-2 by international bodies. Important viral transmission sources include human contact, respiratory droplets and aerosols, and through contact with contaminated objects. However, viral shedding in feces and urine by COVID-19-afflicted patients raises concerns about SARS-CoV-2 entering aquatic systems. Recently, targeted SARS-CoV-2 genome fragments have been successfully detected in wastewater, sewage sludge and river waters around the world. Wastewater-based epidemiology (WBE) studies can provide early detection and assessment of COVID-19 transmission and the growth of active cases within given wastewater catchment areas. WBE surveillance's ability to detect the growth of cases was demonstrated. Was this science applied throughout the world as this pandemic spread throughout the globe? Wastewater treatment efficacy for SARS-CoV-2 removal and risk assessments associated with treated water are reported. Disinfection strategies using chemical disinfectants, heat and radiation for deactivating and destroying SARS-CoV-2 are explained. Analytical methods of SARS-CoV-2 detection are covered. This review provides a more complete overview of the present status of SARS-CoV-2 and its consequences in aquatic systems. So far, WBE programs have not yet served to provide the early alerts to authorities that they have the potential to achieve. This would be desirable in order to activate broad public health measures at earlier stages of local and regional stages of transmission.

Characterization of graphene/pine wood biochar hybrids: Potential to remove aqueous Cu2.

Biochar-based hybrid composites containing added nano-sized phases are emerging adsorbents. Biochar, when functionalized with nanomaterials, can enhance pollutant removal when both the nanophase and the biochar surface act as adsorbents. Three different pine wood wastes (particle size < 0.5 mm, 10 g) were preblended with 1 wt% of three different graphenes in aqueous suspensions, designated as G1, G2, and G3. G1 (SBET, 8.1 m2/g) was prepared by sonicating graphite made from commercial synthetic graphite powder (particle size 7-11 µm). G2 (312.0 m2/g) and G3 (712.0 m2/g) were purchased commercial graphene nanoplatelets (100 mg in 100 mL deionized water). These three pine wood-graphene mixtures were pyrolyzed at 600 °C for 1 h to generate three graphene-biochar adsorbents, GPBC-1, GPBC-2, and GPBC-3 containing 4.4, 4.9, and 5.0 wt% of G1, G2, and G3 respectively. Aqueous Cu2+ adsorption capacities were 10.6 mg/g (GPBC-1), 4.7 mg/g (GPBC-2), and 5.5 mg/g (GPBC-3) versus 7.2 mg/g for raw pine wood biochar (PBC) (0.05 g adsorbent dose, Cu2+ 75 mg/L, 25 mL, pH 6, 24 h, 25 ± 0.5 °C). Increased graphene surface areas did not result in adsorption increases. GPBC-1, containing the lowest nanophase surface area with the highest Cu2+ capacity, was chosen to evaluate its Cu2+ adsorption characteristics further. Results from XPS showed that the surface concentration of oxygenated functional groups on the GPBC-1 is greater than that on the PBC, possibly contributing to its greater Cu2+ removal versus PBC. GPBC-1 and PBC uptake of Cu2+ followed the pseudo-second-order kinetic model. Langmuir maximum adsorption capacities and BET surface areas were 18.4 mg/g, 484.0 m2/g (GPBC-1) and 9.2 mg/g, 378.0 m2/g (PBC). This corresponds to 3.8 × 10-2 versus 2.4 × 10-2 mg/m2 of Cu2+ removed on GPBC-1 (58% more Cu2+ per m2) versus PBC. Cu2+ adsorption on both these adsorbents was spontaneous and endothermic.

Household arsenic contaminated water treatment employing iron oxide/bamboo biochar composite: An approach to technology transfer.

Commercialization of novel adsorbents technology for providing safe drinking water must consider scale-up methodological approaches to bridge the gap between laboratory and industrial applications. These imply complex matrix analysis and large-scale experiment designs. Arsenic concentrations up to 200-fold higher (2000 µg/L) than the WHO safe drinking limit (10 µg/L) have been reported in Latin American drinking waters. In this work, biochar was developed from a single, readily available, and taxonomically identified woody bamboo species, Guadua chacoensis. Raw biochar (BC) from slow pyrolysis (700 °C for 1 h) and its analog containing chemically precipitated Fe3O4 nanoparticles (BC-Fe) were produced. BC-Fe performed well in fixed-bed column sorption. Predicted model capacities ranged from 8.2 to 7.5 mg/g and were not affected by pH 5-9 shift. The effect of competing matrix chemicals including sulfate, phosphate, nitrate, chloride, acetate, dichromate, carbonate, fluoride, selenate, and molybdate ions (each at 0.01 mM, 0.1 mM and 1 mM) was evaluated. Fe3O4 enhanced the adsorption of arsenate as well as phosphate, molybdate, dichromate and selenate. With the exception of nitrate, individually competing ions at low concentration (0.01 mM) did not significantly inhibit As(V) sorption onto BC-Fe. The presence of ten different ions in low concentrations (0.01 mM) did not exert much influence and BC-Fe's preference for arsenate, and removal remained above 90%. The batch and column BC and BC-Fe adsorption capacities and their ability to provide safe drinking water were evaluated using a naturally contaminated tap water (165 ± 5 µg/L As). A 960 mL volume (203.8 Bed Volumes) of As-free drinking water was collected from a 1 g BC-Fe fixed bed. Adsorbent regeneration was attempted with (NH4)2SO4, KOH, or K3PO4 (1 M) strippers. Potassium phosphate performed the best for BC-Fe regeneration. Safe disposal options for the exhausted adsorbents are proposed. Adsorbents and their As-laden analogues (from single and multi-component mixtures) were characterized using high resolution XPS and possible competitive interactions and adsorption pathways and attractive interactions were proposed including electrostatic attractions, hydrogen bonding and weak chemisorption to BC phenolics. Stoichiometric precipitation of metal (Mg, Ca and Fe) oxyanion (phosphate, molybdate, selenate and chromate) insoluble compounds is considered. The use of a packed BC-Fe cartridge to provide As-free drinking water is presented for potential commercial use. BC-Fe is an environmentally friendly and potentially cost-effective adsorbent to provide arsenic-free household water.

Batch and Continuous Fixed-Bed Lead Removal Using Himalayan Pine Needle Biochar: Isotherm and Kinetic Studies.

Pine needle litter in Himalayan forests leads to forest fires, ground water recharge inhibition, soil acidification and contamination, and stops the growth of grass and plants. This study provides a possible solution for pine needle litter problem by converting it to biochar. Pine needle litter lying on the ground for approximately a month was collected from the Himalayan region. The pine needle litter biochars were generated using slow pyrolysis (residence time, 30 min; heating rate, 10 °C/min) at 350, 450, 550, 650, and 750 °C. Finally, pine needle litter biochar prepared at 550 °C (PNBC550) was selected for sorptive removal of aqueous lead both in batch and column studies. The PNBC550 was characterized for proximate and elemental compositions, crystallinity, surface area, morphology, and functional groups. A BET surface area of 230.9 m2/g was obtained for PNBC550. Batch sorption studies were carried out to study (1) the adsorption versus pH studies (at pH 2 to 7), (2) isotherms (at 10, 25, and 35 °C) to evaluate the temperature effect on the sorption efficiency, and (3) kinetics to reveal the effect of time, adsorbent dose, and initial concentration on the reaction rate. Increasing pyrolysis temperature raised lead sorption up to 550 °C. Lead adsorption increased considerably as pH rose from 2 to a maximum adsorption around pH 5 and above. The sorption data were fitted using different isotherm models and kinetic equations. The Langmuir adsorption capacity increased from 22.93 mg/g at 10 °C to 40.43 mg/g at 35 °C, showing that adsorption was endothermic. Fixed-bed studies were conducted at room temperature with an initial lead concentration of 7.85 mg/L and 4.0 g of PNBC550 at initial pH 5.0 and a flow rate of 3 mL/min. Desorption studies conducted under the same experimental conditions found about 90-93% lead recovery. Development of high-efficiency biochars for lead remediation provides a sustainable solution for the Himalayan pine needle litter problem. The biochars also possess the possible potential for aqueous removal of other metal cations.

Rapid remediation of pharmaceuticals from wastewater using magnetic Fe3O4/Douglas fir biochar adsorbents.

Modification of commercially available Douglas fir biochar (BC) by iron oxide nanoparticle precipitation from aqueous Fe2+/Fe3+ salt solutions upon NaOH treatment generated a hybrid adsorbent (MBC) that removed three common emerging aqueous contaminants, a stimulant (caffeine) and two anti-inflammatory drugs (ibuprofen and acetylsalicylic acid) through batch sorption. Fe3O4 particles (12.3 ± 7.1 nm diameter fundamental particles with aggregates 1-17 µm diameter) dispersed on the biochar surface provided magnetization and created new adsorption sites for the contaminant uptake. These smaller quasi-spherical, octahedral Fe3O4 particles as well as the spindle-like Fe2O3 particles were observed with scanning electron microscopy (SEM) images of MBC, and the composition was confirmed by X-ray powder diffraction (XRD). Adsorption features were evaluated using Langmuir and Freundlich isotherm models. The Langmuir adsorption capacities on MBC at 35 °C have increased from 24.6 ± 0.4 to 75.1 ± 1.8 mg/g for caffeine, 17.5 ± 0.4 to 39.9 ± 1.2 mg/g for ibuprofen and 106.2 ± 2.8 to 149.9 ± 4.5 mg/g for acetylsalicylic acid after Fe3O4 modification. Fast adsorption resulted in equilibrium within 5 min. MBC has potential as a low cost, green adsorbent for pharmaceutical mitigation from water with high adsorption capacities and fast kinetics. The Douglas fir biochar is a byproduct waste from a syn-gas from wood production process covering its production costs.

Sustainable Low-Concentration Arsenite [As(III)] Removal in Single and Multicomponent Systems Using Hybrid Iron Oxide-Biochar Nanocomposite Adsorbents-A Mechanistic Study.

Rice and wheat husks were converted to biochars by slow pyrolysis (1 h) at 600 °C. Iron oxide rice husk hybrid biochar (RHIOB) and wheat husk hybrid biochar (WHIOB) were synthesized by copyrolysis of FeCl3-impregnated rice or wheat husks at 600 °C. These hybrid sorbents were characterized using X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), SEM-energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, physical parameter measurement system, and Brunauer-Emmett-Teller (BET) surface area techniques. Fe3O4 was the predominant iron oxide present with some Fe2O3. RHIOB and WHIOB rapidly chemisorbed As(III) from water (∼24% removal in first half an hour reaching up to ∼100% removal in 24 h) at surface Fe-OH functions forming monodentate ≡Fe-OAs(OH)2 and bidentate (≡Fe-O)2AsOH complexes. Optimum removal occurred in the pH 7.5-8.5 range for both RHIOB and WHIOB, but excellent removal occurred from pH 3 to 10. Batch kinetic studies at various initial adsorbate-adsorbent concentrations, temperatures, and contact times gave excellent pseudo-second-order model fits. Equilibrium data were fitted to different sorption isotherm models. Fits to isotherm models (based on R 2 and χ2) on RHIOB and WHIOB followed the order: Redlich-Peterson > Toth > Sips = Koble-Corrigan > Langmuir > Freundlich = Radke-Prausnitz > Temkin and Sips = Koble-Corrigan > Toth > Redlich-Peterson > Langmuir > Temkin > Freundlich = Radke-Prausnitz, respectively. Maximum adsorption capacities, Q RHIOB 0 = 96 µg/g and Q WHIOB 0 = 111 µg/g, were obtained. No As(III) oxidation to As(V) was detected. Arsenic adsorption was endothermic. Particle diffusion was a rate-determining step at low (≤50 µg/L) concentrations, but film diffusion controls the rate at ≥100-200 µg/L. Binding interactions with RHIOB and WHIOB were established, and the mechanism was carefully discussed. RHIOB and WHIOB can successfully be used for As(III) removal in single and multicomponent systems with no significant decrease in adsorption capacity in the presence of interfering ions mainly Cl-, HCO3 -, NO3 -, SO4 2-, PO4 3-, K+, Na+, Ca2+. Simultaneous As(III) desorption and regeneration of RHIOB and WHIOB was successfully achieved. A very nominal decrease in As(III) removal capacity in four consecutive cycles demonstrates the reusability of RHIOB and WHIOB. Furthermore, these sustainable composites had good sorption efficiencies and may be removed magnetically to avoid slow filtration.