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We present an improved method for trace level quantification of five estrogens including estriol, estrone, 17α-estradiol, 17β-estradiol, and 17α-ethinylestradiol in wastewaters. Our method includes sample preparation using SPE followed by a Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) cleanup step, a derivatization, and LC/MS/MS determination. Sample extraction was carried out using Oasis HLB cartridges and a dispersive solid-phase cleanup pack containing MgSO4 and primary-secondary amine and C18 sorbents. The resulting extract was derivatized with dansyl chloride. Separation was achieved on an Agilent Zorbax Extend C18, Narrow Bore RR 2.1 x 100 mm, 3.5 µm column; quantification was accomplished in the positive ion mode using multiple reaction monitoring. The cleanup method is quick, efficient, inexpensive, and requires only 200 mL of water. Reliable linearities were obtained for all calibration curves (r² > 0.995). Matrix effects calculated were less than 12% for all analytes, and, hence, matrix matched calibration curves were not needed. The recoveries for the estrogens ranged from 81-103%, with a high repeatability (n = 3, RSD = 9%) and low LOQs (0.6-0.9 ng/L). The method was used to analyze effluent and influent wastewaters in Mississippi wastewater treatment plants, but it is broadly applicable for the determination of trace estrogens in any municipal wastewater samples. [ABSTRACT FROM AUTHOR]

Abstract: Methyl salicylate (MeS) is used as a chemical warfare agent simulant to test chemical protective garments and other individual personal protective gear. The accurate and real-time detection of this analyte is advantageous for various testing regimes. This paper reports the results of MeS vapor exposures on polymer-filled capacitance-based sensors at temperatures ranging from 15°C to 50°C under dry and humid conditions. Multiple capacitors were arranged in an array on a silicon chip each having a different sorptive polymer. The sensors used parallel-plate electrode geometry to measure the dielectric permittivity changes of each polymer when exposed to water and MeS vapor. Of the four polymers tested against MeS, the optimal polymer displayed near or sub-parts-per-million detection limits at 35°C (0–80%RH). [Copyright &y& Elsevier]

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 Fe 3 O 4 -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 m 2 /g) and large pore volume (∼0.25 cm 3 /g) biochar. Treatment of BC with FeCl 3 /FeSO 4 and NaOH to chemically precipitate Fe 3 O 4 onto BC. BC and its magnetic Fe 3 O 4 /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 Fe 3 O 4 /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 Fe 3 O 4 /BC analogue are adsorbent candidates for PFAS remediation from the dilute PFAS concentrations often found in polluted environments. Small Fe 3 O 4 /BC particles can be magnetically removed from batch treatments avoiding filtration., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This is the first report of the metal Fe-Ti oxide/biochar (Fe 2 TiO 5 /BC) composite for simultaneous removal of aqueous Pb 2+ , Cr 6+ , F - and methylene blue (MB). Primary Fe 2 TiO 5 nano particles and aggregates were dispersed on a high surface area Douglas fir BC (∼700 m 2 /g) by a simple chemical co-precipitation method using FeCl 3 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 Fe 2 TiO 5 , exhibiting a lower energy band gap than TiO 2 . Adsorption of Cr(VI), Pb(II), fluoride, and MB on Fe 2 TiO 5 /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 Pb 2+ , Cr 6+ , 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 Fe 2 TiO 5 /BC by synergistic adsorption and photocatalytic degradation at pH 3 and 6 under UV (365 nm) light irradiation. Cr 6+ , Pb 2+ , F - , and MB each exhibited excellent removal capacities in the presence of eight different competitive ions in simulated water samples. The removal mechanisms on Fe 2 TiO 5 /BC and various competitive ion interactions were proposed. Some iron ion leaching at pH 3 catalyzed Photo-Fenton destruction of MB. Fe 2 TiO 5 , BC, and Fe 2 TiO 5 /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 TiO 2 for water treatment. A long range goal is to photocatalytically destroy some sorbates with adsorbents to avoid the need for regeneration steps., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

This study compared the lead (Pb 2+ ) 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 Pb 2+ immobilized was determined by comparing the concentration of ammonium nitrate extractable Pb 2+ 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 NH 4 NO 3 -extractable Pb 2+ , while lead-spiked soil treated with 5% (wt./wt.) biochar-supported phosphate resulted in the lowest quantity of NH 4 NO 3 extractable Pb 2+ (0.3 ± 0.2 mg L -1 ). The mechanism for immobilization of Pb 2+ by BP occurs at pH < 7 through dissolution of hydroxyapatite embedded in BP during modification, followed by precipitation of insoluble Pb 10 (PO 4 ) 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 Pb 2+ uptake into plants while minimizing the potential for water contamination due to Pb 2+ mobility., (Published by Elsevier Ltd.)

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 m 2 /g BET (N 2 ) 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., (Published by Elsevier Ltd.)

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 m 2 /g surface area and 0.26 cm 3 /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 (CO 3 2- , AsO 4 3- , SeO 4 2- , NO 3 - , Cr 2 O 7 2- , Cl - , F - , SO 4 2- , and MoO 4 2- ) 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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

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 Fe 3 O 4 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. Fe 3 O 4 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 (NH 4 ) 2 SO 4 , KOH, or K 3 PO 4 (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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Modification of commercially available Douglas fir biochar (BC) by iron oxide nanoparticle precipitation from aqueous Fe 2+ /Fe 3+ 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. Fe 3 O 4 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 Fe 3 O 4 particles as well as the spindle-like Fe 2 O 3 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 Fe 3 O 4 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Ltd.)

Discarded bamboo culms of Guadua chacoensis were used for biochar remediation of aqueous As(V). Raw biochar (BC), activated biochar (BCA), raw Fe 3 O 4 nanoparticle-covered biochar (BC-Fe), and activated biochar covered with Fe 3 O 4 nanoparticles (BCA-Fe) were prepared, characterized and tested for As(V) aqueous adsorption. The goal is to develop an economic, viable, and sustainable adsorbent to provide safe arsenic-free water. Adsorbents were characterized using scanning electron microscopy (SEM) and energy dispersive analysis by X-ray (SEM-EDX), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (TEM-EDS), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller surface area measurements (S BET ), point of zero charge determinations (PZC), and elemental analysis. Activation with KOH increased the O/C ratio and the surface area of BC from 6.7 m 2 /g to 1239.7 m 2 /g (BCA). As(V) sorption equilibrium was achieved within <2 h for all four adsorbents and kinetics followed the pseudo-second-order model. At a 10 mg/L initial As(V) concentration, BC-Fe achieved a 100% removal (5 mg/g) over a pH 5 to 9 window. Sorption was endothermic on all four adsorbents and the capacities rose with the increasing temperature. Langmuir capacities at 40 °C for BC, BCA, BC-Fe, and BCA-Fe were 256, 217, 457, and 868 mg/g, respectively, and capacities were compared with other sorbents. Breakthrough fixed-bed column sorption was carried out for BC and BC-Fe producing 6.6 mg/g and 13.9 mg/g bed capacities, respectively. Potassium phosphate was a better As stripping agent than sodium bicarbonate. Performance of the adsorbents in an As(V)-spiked natural water and a naturally As(V)-contaminated domestic water were assessed. Robust arsenate sequestration occurred generating As-safe water (As <0.01 mg/L), despite the presence of competing ions. Stoichiometric precipitation of iron-arsenate complexes triggered by iron dissolution was also established., (Copyright © 2019. Published by Elsevier B.V.)

Magnetic Fe 3 O 4 /Douglas fir biochar composites (MBC) were prepared with a 29.2% wt. Fe 3 O 4 loading and used to treat As(III)-contaminated water. Toxicity of As(III) (inorganic) is significantly greater than As(V) and more difficult to remove from water. Removal efficiency was optimized verses pH, contact time and initial concentration. Column sorption and regeneration were also studied. Adsorption kinetics data best fitted the pseudo second order model (R 2  > 0.99). Adsorption was analyzed with three isotherm models at 20, 25 and 40 °C. The Sips isotherm showed the best fit at 25 °C with a 5.49 mg/g adsorption capacity, which is comparable with other adsorbents. MBC gave faster kinetics (~1-1.5 h) at pH 7 and ambient temperature than previous adsorbents. The Gibbs free energy (ΔG) of this spontaneous As(III) adsorption was -35 kJ/mol and ΔH = 70 kJ/mol was endothermic. Experiments were performed on industrial and laboratory wastewater samples in the presence of other co-existing contaminants (pharmaceutical residues, heavy metals ions and oxi-anions). The composite reduced the arsenic concentrations below the WHO's safe limit of 0.2 mg/L for waste water discharge. X-ray photoelectron spectroscopy (XPS) studies found As(III) and less toxic As(V) on Fe 3 O 4 surfaces indicating adsorbed (or adsorbing) As(III) oxidation occurred upon contact with O 2 and possibly dissolved Fe(III) or upon drying under oxic conditions. Under anoxic conditions magnetite to maghemite transformation drives the oxidation. A pH-dependent surface chemisorption mechanism was proposed governing adsorption aided by XPS studies vs pH., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

α-Fe 2 O 3 and Fe 3 O 4 dispersed on high surface area (663 m 2 /g) Douglas fir biochar (BC) was prepared for fast nitrate and fluoride ion removal from water using magnetic separations. This biochar, made originally at 900 °C, was impregnated with FeCl 3 and converted by pyrolysis at 600 °C to magnetic (494 m 2 /g) biochar (MBC). MBC and its precursor BC were characterized using SEM, SEM-EDX, STEM, S BET , PZC measurements, XRD analysis, and XPS. Dispersed α-Fe 2 O 3 and Fe 3 O 4 particles caused magnetization and generated most adsorption sites, causing more nitrate and fluoride uptake than BC. Both nitrate and fluoride adsorption on MBC remained high over a pH range from 2 to 10. Sorption was evaluated from 298 to 318 K using the Langmuir and Freundlich isotherm models. Langmuir adsorption capacities were 15 mg/g for nitrate and 9 mg/g for fluoride, higher capacities than those reported for other biochar and iron oxide adsorbents., (Published by Elsevier Ltd.)

Chitosan-Modified fast pyrolysis BioChar (CMBC) was used to remove Pb 2+ from water. CMBC was made by mixing pine wood biochar with a 2% aqueous acetic acid chitosan (85% deacylated chitin) solution followed by treatment with NaOH. The characterizations of both CMBC and Non-Modified BioChar (NMBC) were done using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), scanning electron microscopy (SEM), surface area measurements ( S BET ), elemental analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and ζ-potential measurements. Elemental analysis indicated that chitosan accounts for about 25% weight of the CMBC. The Langmuir maximum adsorption capacity of CMBC at pH 5 was 134 mg g -1 versus 48.2 mg g -1 for NMBC at 318 K. CMBC column adsorption studies resulted in a capacity of 5.8 mg g -1 (Pb 2+ conc. 150 mg L -1 ; pH 5; column dia 1.0 cm; column length 20 cm; bed height 5.0 cm; flow rate 2.5 mL min -1 ). CMBC removed more Pb 2+ than NMBC suggesting that modification with chitosan generates amine groups on the biochar surface which enhance Pb 2+ adsorption. The modes of Pb 2+ adsorption on CMBC were studied by comparing DRIFTS and X-ray photoelectron spectroscopy spectra before and after Pb 2+ adsorption., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Utilization of biochar (BC) as a low cost adsorbent for water remediation has gained an immense research interest due to their surface functionality and porosity. Although many reports on the BC based sorptive removal of Sulfonamides (SA) and Tetracyclines (TC) are available in literature, a deep insight into sorption mechanisms is yet to be reviewed. Objective of this review is to fill the research gap of a methodological understanding of sorption mechanisms and characteristics which is essential to develop efficient methods for contaminant removal. The most common adsorption mechanism can be considered as electron donor-acceptor interactions of electron withdrawing moieties with surface arene rings. The strongest adsorption of both antibiotics occurs at mildly acidic pH where the dominant species are zwitterionic or cationic. Smaller SAs exhibit micro pore-filling effects while bulky TCs experience size exclusions. Furthermore, the effect of matrix components and modifications are also been taken into account., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A regioselective synthesis of 6-alkyl- and 6-aryluracils was developed by the dimerization of 3-alkyl- and 3-aryl-2-propynamides promoted by either Cs 2 CO 3 or K 3 PO 4 . A range of 3-aryl-2-propynamides, with both electron-deficient and electron-rich 3-aryl substituents, were successfully reacted in high yields. Cs + acts as a soft Lewis acid to polarize the carbon-carbon triple bond, and solid K 3 PO 4 interacts with carbonyl oxygen, promoting intermolecular nucleophilic attack by the only weakly nucleophilic amide nitrogen. Experiments were conducted to support the proposed mechanism.