HS-BAµE: A New Alternative Approach for VOCs Analysis-Application for Monitoring Biogenic Emissions from Tree Species.

In this work, a new analytical approach is proposed for monitoring biogenic volatile organic compounds (BVOCs) by combining headspace bar adsorptive microextraction (HS-BAµE) with gas chromatography-mass spectrometry (GC-MS). The HS-BAµE methodology was developed, optimized, validated and applied for the analysis of BVOCs emitted from two tree species (Eucalyptus globulus Labill. and Pinus pinaster Aiton) and compared with headspace solid phase microextraction (HS-SPME), commonly accepted as a reference technique. To achieve optimum experimental conditions, numerous assays were carried out by both methodologies, studying the release of the five major monoterpenoids (α-pinene, ß-pinene, myrcene, limonene and 1,8-cineole) from the leaves of the tree species, whereas the maximum selectivity and efficiency were obtained using an activated carbon and PDMS/DVB fiber as sorbent phases for HS-BAµE and HS-SPME, respectively. Under optimized experimental conditions, both methodologies showed similar profiling and proportional responses, although the latter present a higher sensitivity in the analytical configuration used. For the five monoterpenoids studied, acceptable detection limits (LODs = 5.0 µg L-1) and suitable linear dynamic ranges (20.0-100.0 mg L-1; r2 ≥ 0.9959) were achieved, and intra- and inter-day studies proved that both methodologies exhibited good results (RSD and %RE ≤ 19.9%), which indicates a good fit for the assessment of BVOCs by the HS-BAµE/GC-MS methodology. Assays performed on sampled leaves by both optimized and validated methodologies showed high levels of the five major BVOCs released from E. globulus Labill. (10.2 ± 1.3 to 7828.0 ± 40.0 µg g-1) and P. pinaster Aiton (9.2 ± 1.4 to 3503.8 ± 396.3 µg g-1), which might act as potential fuel during forest fire's propagation, particularly under extreme atmospheric conditions. This is the first time that BAµE technology was applied in the HS sampling mode, and, in addition to other advantages, it has proven to be an effective and promising analytical alternative for monitoring VOCs, given its great simplicity, easy handling and low cost.

Steam Activation of Acid-Chars for Enhanced Textural Properties and Pharmaceuticals Removal.

The present work aims to explore steam activation of sisal or glucose-derived acid-chars as an alternative to KOH activation to prepare superactivated carbons, and to assess the adsorption performance of acid-chars and derived activated carbons for pharmaceuticals removal. Acid-chars were prepared from two biomass precursors (sisal and glucose) using various H2SO4 concentrations (13.5 M, 12 M, and 9 M) and further steam-activated at increasing burn-off degrees. Selected materials were tested for the removal of ibuprofen and iopamidol from aqueous solution (kinetic and equilibrium assays) in single-solute conditions. Activated carbons prepared from acid-char carbonized with 13.5 M and 12 M H2SO4 are mainly microporous solids composed of compact rough particles, yielding a maximum surface area and a total pore volume of 1987 m2 g-1 and 0.96 cm3 g-1, respectively. Solid state NMR reveals that steam activation increased the aromaticity degree and amount of C=O functionalities. Steam activation improved the acid-chars adsorption capacity for ibuprofen from 20-65 mg g-1 to higher than 280 mg g-1, leading to fast adsorption kinetics (15-20 min). The maximum adsorption capacities of selected activated samples for ibuprofen and iopamidol were 323 and 1111 mg g-1, respectively.

Engineered pine nut shell derived activated carbons for improved removal of recalcitrant pharmaceuticals in urban wastewater treatment.

Novel powdered activated carbons (PACs) from pine cones and pine nut shells (PNSs) were tested for the competitive adsorption of pharmaceutical compounds (PhCs) in spiked (100 µg/L) secondary effluent and mixed liquor from an urban wastewater treatment plant. Steam activated PNS77, with hierarchical pore structure and 1463 m2/g of BET area, outperformed the commercial benchmark (WP220, mineral origin) for PhCs and dissolved organic matter (DOM) control. PNS77 attained the highest adsorption capacity and rate in synthetic and real wastewaters. Competitive adsorption isotherms revealed the detrimental effect of direct site competing DOM on PhC removal. The PhCs' adsorbability increased with their hydrophobicity, regardless of the water matrix. Kinetic data allowed inferring that indirect competition due to pore constriction/blockage appeared to occur only in mixed liquor. Adsorption isotherm data modelling for ng/L range revealed 80 % removal of carbamazepine and diclofenac would be achieved dosing 8-15 mg/L PNS77 to secondary effluent, while for mixed liquor the dose must be doubled to balance the increased competition. Hydrophilic sulfamethoxazole required a higher dose (34-44 mg/L), lower in the mixed liquor. PNS77 hierarchical pore network and basic surface chemistry minimized DOM direct site competition, requiring lower doses in practical applications for wastewater treatment.

Solar Light-Induced Methylene Blue Removal over TiO2/AC Composites and Photocatalytic Regeneration.

TiO2-containing photocatalysts, which combine TiO2 with carbon-based materials, are promising materials for wastewater treatment due to synergistic photodegradation and adsorption phenomena. In this work, TiO2/AC composites were produced by the in situ immobilization of TiO2 nanoparticles over activated carbon (AC) derived from spent coffee grains, using different TiO2/AC proportions. The TiO2/AC composites were tested as adsorbents (dark) and as photocatalysts in a combined adsorption+photocatalytic process (solar irradiation) for methylene blue (MB) removal from ultrapure water, and from a secondary effluent (SecEf) of an urban wastewater treatment plant. All the materials were characterized by XRD (X-ray powder diffraction), N2 adsorption-desorption isotherms at -196 °C, SEM (scanning electron microscopy), UV-Vis diffuse reflectance, FTIR (Fourier-transform infrared spectroscopy), TPD (temperature programmed desorption), XPS (X-ray photoelectron spectroscopy) and TGA (thermogravimetric analysis). The TiAC60 (60% C) composite presented the lowest band gap (1.84 eV), while, for TiAC29 (29% C), the value was close to that of bare TiO2 (3.18 vs. 3.17 eV). Regardless of the material, the solar irradiation improved the percentage of MB discolouration when compared to adsorption in dark conditions. In the case of simultaneous adsorption+photocatalytic assays performed in ultrapure water, TiAC29 presented the fastest MB removal. Nevertheless, both TiAC29 and TiAC60 led to excellent MB removal percentages (96.1-98.1%). UV-induced photoregeneration was a promising strategy to recover the adsorption capacity of the materials, especially for TiAC60 and AC (>95%). When the assays were performed in SecEf, all the materials promoted discolouration percentages close to those obtained in ultrapure water. The bulk water parameters revealed that TiAC60 allowed the removal of a higher amount of MB, associated with the overall improvement of the SecEf quality.

Assessing the applicability of a new carob waste-derived powdered activated carbon to control pharmaceutical compounds in wastewater treatment.

This paper assesses the applicability of a new carob waste-derived powdered activated carbon (PAC) obtained by steam activation for pharmaceutical compounds (PhCs) removal in urban wastewater treatment plants (WWTPs) with activated sludge (AS) secondary treatment. The new carob-derived PAC presents chemical and textural properties similar to a high-performing commercial PAC produced from vegetable source by physical activation. The adsorption isotherms of three target PhCs, carbamazepine, diclofenac and sulfamethoxazole, spiked (at around 100 µg/L) in mixed liquor (ML) and in clarified-ML from the AS-bioreactor of a WWTP show: (i) minor reduction of PAC capacity with real MLs compared to clarified MLs; (ii) the higher the PhC hydrophobicity, the higher the PAC adsorption capacity in both water matrices; (iii) hydrophobic interactions probably overweight electrostatic interactions between the PhCs and the slightly positively charged PAC in these real water matrices with background organics and inorganics. The PhC adsorption results with ML and clarified-ML are used to calibrate the IAST-based tracer model (TRM) and predict the new PAC performance when added to AS-bioreactor vs. in post-secondary treatment, at the PhC naturally-occurring trace concentrations. The modelling projections show (i) one needs higher PAC doses than those reported in the literature, particularly in post-treatment, and (ii) the benefits of PAC dosing to the bioreactor, with only a slightly higher PAC dose being needed when compared to its post-secondary dosing and minimising the capital investment.

Carbon-Based Sorbent Coatings for the Determination of Pharmaceutical Compounds by Bar Adsorptive Microextraction.

Thirteen carbon materials comprising commercial activated carbons and lab-made materials (activated carbons, hydrochars, and low-T and high-T activated hydrochars) were assayed as sorbent coatings in bar adsorptive microextration (BAµE) to monitor trace levels of ten common pharmaceutical compounds (PhCs) in environmental water matrices including surface water, seawater, tap water, and wastewater. Polar and nonpolar pharmaceuticals were selected, sulfamethoxazole, triclosan, carbamazepine, diclofenac, mefenamic acid, 17-α-ethinylestradiol, 17-ß-estradiol, estrone, gemfibrozil, and clofibric acid, as model compounds to cover distinct therapeutic classes. Despite having a less-developed porosity, data showed that "in-house" prepared low-T activated hydrochars, obtained from carbohydrates and an eutectic salt mixture at low temperature (i.e., 180 °C) and autogenerated pressure, compete with the best commercial activated carbons for this particular application. The combination of a micro and mesopore network with a rich oxygen-based surface chemistry yielding an acidic nature allowed these low-T activated hydrochars to present the best overall recoveries (between 20.9 and 82.4%) for the simultaneous determination of the ten target PhCs with very distinct chemical properties using high performance liquid chromatography-diode array detection (HPLC-DAD).

Photocatalytic Degradation of Pharmaceuticals Carbamazepine, Diclofenac, and Sulfamethoxazole by Semiconductor and Carbon Materials: A Review.

The presence of pharmaceutical compounds in the environment is a reality that calls for more efficient water treatment technologies. Photocatalysis is a powerful technology available but the high energy costs associated with the use of UV irradiation hinder its large scale implementation. More sustainable and cheaper photocatalytic processes can be achieved by improving the sunlight harvesting and the synthesis of semiconductor/carbon composites has proved to be a promising strategy. Carbamazepine, diclofenac, and sulfamethoxazole were selected as target pharmaceuticals due to their recalcitrant behavior during conventional wastewater treatment and persistence in the environment, as properly reviewed. The literature data on the photocatalytic removal of carbamazepine, diclofenac, and sulfamethoxazole by semiconductor/carbon materials was critically revised to highlight the role of the carbon in the enhanced semiconductor performance under solar irradiation. Generally it was demonstrated that carbon materials induce red-shift absorption and they contribute to more effective charge separation, thus improving the composite photoactivity. Carbon was added as a dopant (C-doping) or as support or doping materials (i.e., nanoporous carbons, carbon nanotubes (CNTs), graphene, and derived materials, carbon quantum dots (CQDs), and biochars) and in the large majority of the cases, TiO2 was the semiconductor tested. The specific role of carbon materials is dependent on their properties but even the more amorphous forms, like nanoporous carbons or biochars, allow to prepare composites with improved properties compared to the bare semiconductor. The self-photocatalytic activity of the carbon materials was also reported and should be further explored. The removal and mineralization rates, as well as degradation pathways and toxicity of the treated solutions were also critically analyzed.

Chemically activated high grade nanoporous carbons from low density renewable biomass (Agave sisalana) for the removal of pharmaceuticals.

HYPOTHESIS: Enlarging the range of viable nanoporous carbon precursors, namely by the acid treatment of low density biomass residues, can overcome issues related with the availability and quality of raw materials that have potential impact on cost and quality grade of the final product. EXPERIMENTS: Nanoporous carbons were prepared following a two-step process: H2SO4 digestion/polycondensation of biomass waste (Agave sisalana, sisal) at temperature below 100 °C and atmospheric pressure to obtain acid-chars that were further chemically activated with KOH or K2CO3. Selected synthesized nanoporous carbons were tested for the removal of pharmaceutical compounds - ibuprofen and iopamidol - in aqueous solutions. FINDINGS: The structure and density of the acid-chars are highly dependent on the concentration of H2SO4 used in the digestion and polycondensation steps. An adequate choice of the acid-char synthesis conditions, activating agent and contact method allowed to feature nanoporous carbons with specific surface areas ranging from 600 to 2300 m2 g-1 and apparent densities reaching 600 kg m-3. The adsorption capacity of a sample obtained by KOH-activation for the removal of micropollutants from water was twice higher than the value attained by a golden activated carbon (Cabot-Norit) commercialized for this specific purpose.

Designing micro- and mesoporous carbon networks by chemical activation of organic resins.

Carbon xerogels with ultrahigh micro- and mesopore volumes were synthesized from the activation of polymeric resins prepared by sol-gel polycondensation of resorcinol/formaldehyde mixtures in basic medium and subcritical drying. Various activating conditions (e.g., agent, temperature, impregnation conditions) were used and it was found that the textural features of the resulting carbon xerogels are linked to the experimental procedure of the activation reaction to promote the porosity development. The shrinkage and structural collapse of the fragile resins typically obtained upon annealing at high temperatures (during carbonization and/or physical activation) is suppressed when the impregnation of the chemical activating agent is performed under controlled conditions. If the alkaline reagent (either KOH or K2CO3) is put in contact with the resin by wet impregnation (liquid/solid); under such conditions, the intimate contact between both compounds allows the formation of microporosity during the activation along with the enlargement and/or preservation of the mesoporosity of the pristine resin. Furthermore, the chemical activation via wet impregnation allows the combination of high surface areas and the preservation (even higher development) of the mesoporosity created during the synthesis of the resin. The effect of the impregnation method was found highly dependent of the reagent and activation temperature, highlighting the possibility to design micro-mesoporous carbon xerogels at low temperatures with a subtle control of the activation conditions.

The influence of the textural properties of activated carbons on acetaminophen adsorption at different temperatures.

The influence of temperature (20-40 °C) on the acetaminophen adsorption onto activated carbons with different textures was studied. Different temperature dependences, not explained by kinetic effects, were observed for carbons with different micropore size distribution patterns: adsorption capacity increased for pine gasification residues (Pi-fa) derived carbons and decreased for sisal based materials. No significant variation was seen for carbon CP. The species identified by (1)H NMR spectroscopy on the back-extraction solution proved that during the adsorption process exist the conditions required to promote the formation of acetaminophen oligomers which have constrained access to the narrow microporosity. The rotation energy of the dihedral angle between monomers (estimated by electronic DFT methods) showed that conformations in the planar form are less stable than the non-planar conformation (energy barrier of 70 and 23 kJ mol(-1)), but have critical dimensions similar to the monomer and can access most of the micropore volume. The enthalpy change of the overall process showed that the energy gain of the system (endothermic) for Pi-fa samples (≈40 kJ mol(-1)) was enough to allow a change in the dimer, or even a larger oligomer, conformation to the planar form. This will permit adsorption in the narrow micropores, thus explaining the uptake increase with temperature. Non-continuous micropore size distributions centered at pore widths close to the critical dimensions of the planar form seem to be crucial for a positive evolution of the adsorption capacity with temperature.

Chars from gasification of coal and pine activated with K2CO3: acetaminophen and caffeine adsorption from aqueous solutions.

The high carbon contents and low toxicity levels of chars from coal and pine gasification provide an incentive to consider their use as precursors of porous carbons obtained by chemical activation with K2CO3. Given the chars characteristics, previous demineralization and thermal treatments were made, but no improvement on the solids properties was observed. The highest porosity development was obtained with the biomass derived char (Pi). This char sample produced porous materials with preparation yields near 50% along with high porosity development (ABET≈1500m(2)g(-1)). For calcinations at 800°C, the control of the experimental conditions allowed the preparation of samples with a micropore system formed almost exclusively by larger micropores. A mesopore network was developed only for samples calcined at 900°C. Kinetic and equilibrium acetaminophen and caffeine adsorption data, showed that the processes obey to a pseudo-second order kinetic equation and to the Langmuir model, respectively. The results of sample Pi/1:3/800/2 outperformed those of the commercial carbons. Acetaminophen adsorption process was ruled by the micropore size distribution of the carbons. The caffeine monolayer capacities suggest a very efficient packing of this molecule in samples presenting monomodal micropore size distribution. The surface chemistry seems to be the determinant factor that controls the affinity of caffeine towards the carbons.

Activated carbons from sisal waste by chemical activation with K2CO3: kinetics of paracetamol and ibuprofen removal from aqueous solution.

Sisal waste was used as precursor to prepare carbons by chemical activation. The influence of the K(2)CO(3) amount and activation temperature on the materials textural properties were studied through N(2) and CO(2) adsorption assays. As the severity of the treatment increases there is a development of supermicropores, and the micropore size distribution changes from mono to bimodal. A carbon with an apparent surface area of 1,038 m(2)g(-1) and pore volume of 0.49 cm(3)g(-1) was obtained. TPD results showed the incidence in acidic type groups although the pH(PZC) reveals an almost neutral character of the surface. Adsorption kinetic data of ibuprofen and paracetamol show that the processes obey to a pseudo-second order kinetic equation. Regarding the removal efficiency the prepared samples attained values comparable to a commercial carbon (>65%), revealing that chemical activation of sisal wastes with K(2)CO(3) allows obtaining samples suitable for pharmaceutical compounds removal from liquid phase.

Waste-derived activated carbons for removal of ibuprofen from solution: role of surface chemistry and pore structure.

The removal of a widespread used drug (i.e., ibuprofen) from water was investigated using high valuable carbon adsorbents obtained from chemical and physical activation of a bioresource (cork) and a municipal waste (plastic). The waste-derived carbons outperformed the adsorption capacity of commercial carbonaceous adsorbents due to their adequate features for the removal of the targeted compound. Regarding the adsorption mechanism, the results obtained point out that ibuprofen retention is favored in activated carbons with basic surface properties. On the other hand, the textural features also play an important role; the presence of a transport pores network (i.e., mesopores) is crucial to ensure the accessibility to the inner porosity, and the microporosity must be large enough to accommodate the ibuprofen molecule. Specifically, adsorbents with a large fraction of ultramicropores (pore widths <0.7 nm) are not adequate to effectively remove ibuprofen.