Enhanced degradation of organic contaminants using catalytic activity of carbonaceous structures: A strategy for the reuse of exhausted sorbents.

Generation of hydroxyl radicals (⋅OH) is the basis of advanced oxidation process (AOP). This study investigates the catalytic activity of microporous carbonaceous structure for in-situ generation of ⋅OH radicals. Biochar (BC) was selected as a representative of carbon materials with a graphitic structure. The work aims at assessing the impact of BC structure on the activation of H2O2, the reinforcement of the persistent free radicals (PFRs) in BC using heavy metal complexes, and the subsequent AOP. Accordingly, three different biochars (raw, chemically- and physiochemically-activated BCs) were used for adsorption of two metal ions (nickel and lead) and the degradation of phenol (100 mg/L) through AOP. The results demonstrated four outcomes: (1) The structure of carbon material, the identity and the quantity of the metal complexes in the structure play the key roles in the AOP process. (2) the quantity of PFRs on BC significantly increased (by 200%) with structural activation and metal loading. (3) Though the Pb-loaded BC contained a larger quantity of PFRs, Ni-loaded BC exhibited a higher catalytic activity. (4) The degradation efficiency values for phenol by modified biochar in the presence of H2O2 was 80.3%, while the removal efficiency was found to be 17% and 22% in the two control tests, with H2O2 (no BC) and with BC (no H2O2), respectively. Overall, the work proposes a new approach for dual applications of carbonaceous structures; adsorption of metal ions and treatment of organic contaminants through in-situ chemical oxidation (ISCO).

Modulation of Cytochrome P450, P-glycoprotein and Pregnane X Receptor by Selected Antimalarial Herbs-Implication for Herb-Drug Interaction.

Seven medicinal plants popularly used for treating malaria in West Africa were selected to assess herb-drug interaction potential through a series of in vitro methods. Fluorescent cytochrome P450 (CYP) assays were conducted using the recombinant CYP enzymes for CYP1A2, CYP2A6, CYP2B6, CYP2C9, CYP2C19, CYP2D6 and CYP3A4 to assess the effect of the methanolic extracts on the metabolic activity of CYPs. Secondly, the inhibitory effect of the extracts was evaluated on P-glycoproteins (P-gp) using calcein-AM, a fluorescent substrate, in MDCK-II and hMDR1-MDCK-II cells. The inhibition of P-gp activity was determined as a reflection of increase in calcein-AM uptake. Additionally, the enzyme induction potential of the extracts was assessed through the modulation of PXR activity in HepG2 cells transiently transfected with pSG5-PXR and PCR5 plasmid DNA. Significant inhibition of CYP activity (IC50 < 10 µg/mL) was observed with the following herbs: A. muricata [CYP2C9, 3A4 and CYP2D6]; M. indica [CYP2C9]; M. charantia [CYP2C9 and CYP2C19]; P. amarus [CYP2C19, CYP2C9 and CYP3A4]; T. diversifolia [CYP2C19 and CYP3A4]. Extracts of four herbs (P. amarus, M. charantia, T. diversifolia and A. muricata) exhibited significant inhibition of P-gp with IC50 values (µg/mL) of 17 ± 1, 16 ± 0.4, 26 ± 1, and 24 ± 1, respectively. In addition, four herbs (A. mexicana, M. charantia, P. amarus and T. diversifolia) showed a >two-fold increase in induction in PXR activity. These findings suggest that these herbs may be capable of eliciting herb-drug interactions if consumed in high quantities with concomitant use of conventional therapies.

Design, synthesis and in vitro cell-based evaluation of the anti-cancer activities of hispolon analogs.

Phytochemicals play an important role in cancer therapy. Hispolon and 26 of its analogs (9 known and 17 new) were synthesized and evaluated for their antiproliferative activities in a panel of six independent human cancer cell lines using the in vitro cell-based MTT assay. Among the hispolon analogs tested, compound VA-2, the most potent overall, produced its most significant effect in the colon cancer cell lines HCT-116 (IC50 1.4 ± 1.3 µM) and S1 (IC50 1.8 ± 0.9 µM) compared to its activity in the normal HEK293/pcDNA3.1 cell line (IC50 15.8±3.7 µM; p<0.01 for each comparison). Based on our results, VA-2 was about 9- to 11-times more potent in colon cancer cells and 2- to 3-times more potent in prostate cancer cells compared to HEK293/pcDNA3.1 cells. Morphological analysis of VA-2 showed significant reduction of cell number, while the cells' sizes were also markedly increased and were obvious at 68 h of treatment with 1 µM in HCT-116 (colon) and PC-3 (prostate) cancer cells. A known analog, compound VA-4, prepared by simple modifications on the aromatic functional groups of hispolon, inhibited prostate and colon cancer cell lines with IC50 values <10 µM. In addition, hispolon isoxazole and pyrazole analogs, VA-7 and VA-15 (known), respectively, have shown significant activity with the mean ICv values in the range 3.3-10.7 µM in all the cancer cell lines tested. Activity varied among the analogs in which aromatic functional groups and ß-diketone functional groups are modified. But the activity of analogs VA-16 to VA-27 was completely lost when the side chain double-bond was hydrogenated indicating the crucial role of this functionality for anticancer activity. Furthermore, many of the compounds synthesized were not substrates for the ABCB1-transporter, the most common cause of multidrug resistance in anti-cancer drugs, suggesting they may be more effective anticancer agents.

Sorption studies of Cr(VI) from aqueous solution using bio-char as an adsorbent.

The characteristics of sorption of hexavalent chromium (Cr(VI)) onto bio-char derived from wood chips (spruce, pine, and fir) were evaluated as a function of pH, initial Cr(VI) concentration and bio-char dosage using synthetic wastewater in batch tests. The initial Cr(VI) concentrations were varied between 10 and 500 mg/L to investigate equilibrium, kinetics, and isotherms of the sorption process. About 100% of Cr(VI) was removed at pH 2 with initial Cr(VI) concentration of 10 mg/L using 4 g of bio-char after 5 hours of sorption reaction. The maximum sorption capacity of the bio-char was 1.717 mg/g for an initial Cr(VI) concentration of 500 mg/L after 5 hours. The sorption kinetics of total Cr onto bio-char followed the second-order kinetic model. The Langmuir isotherm model provided the best fit for total Cr sorption onto bio-char. The bio-char used is a co-product of a down draft gasifier that uses the derived syngas to produce electricity. Bio-char as a low cost adsorbent demonstrated promising results for removal of Cr(VI) from aqueous solution. The findings of this study would be useful in designing a filtration unit with bio-char in a full-scale water and wastewater treatment plant for the Cr(VI) removal from contaminated waters.

Activation of sawdust biochar with water and wastewater treatment residuals for sorption of perfluorooctanesulfonic acid in water.

Recent research has found biochar to be a cost-effective adsorbent for removal of perfluoroalkyl substances in water. To promote cleaner production and sustainable waste management, this study explored the potential to produce activated biochars by co-pyrolyzing sawdust with iron-rich biosolids and polyaluminum sludge. The maximum capacity to adsorb perfluorooctanesulfonic acid (PFOS) reached 27.2 mg g-1 with biosolids-activated biochar and 19.2 mg g-1 with aluminum sludge-activated biochar, compared to 6.2 mg g-1 with sawdust biochar. The increased adsorption capacities were attributed to electrostatic interactions between the anionic PFOS and metal functionalities on the biochar surface. In contrast, hydrophobic interaction was the dominant adsorption mechanism of sawdust biochar. The presence of dissolved organic matter at 5-50 mg L-1 was found to inhibit adsorption of PFOS in water, while pH as low as 3.0 and sodium chloride concentrations up to 100 mM enhanced removal of PFOS by all the three adsorbents. In batch adsorption tests at environmentally relevant PFOS dosages and adsorbent dosage of 0.25 g L-1, the biosolids-sawdust biochar and Al sludge-sawdust biochar removed 71.4% and 66.9% of PFOS from drinking water and 77.9% and 87.9% of PFOS from filtrate of sludge digestate, respectively. The biosolids-sawdust biochar additionally removed Fe, although the Al sludge-sawdust biochar released Al into the alkaline drinking water and filtrate. Overall, this study proved co-pyrolyzing sawdust and Fe-rich biosolids to be an effective approach to activate sawdust biochar for enhanced removal of PFOS while recycling wastewater treatment residuals and sawdust.

Capacitive Removal of Pb ions via Electrosorption on Novel Willow Biochar - Manganese Dioxide Composites.

AbstractBiochar derived from lignocellulosic biomass has been used as a low-cost adsorbent in wastewater treatment applications. Due to its rich porous structure and good electrical conductivity, biochar can be used as a cost-effective electrode material for capacitive deionization of water. In this work, willow biochar was prepared through carbonization of shrub willow chips, activated with potassium hydroxide, and loaded with manganese dioxide (WBC-K-MnO2 nanocomposite). The prepared materials were used to electrochemically adsorb Pb2+ from aqueous solutions. Under the applied potential of 1.0 V, the WBC-K-MnO2 electrode exhibited a high Pb2+ specific electrosorption capacity (23.3 mg/g) as compared to raw willow biochar (4.0 mg/g) and activated willow biochar (9.2 mg/g). KOH activation followed by MnO2 loading on the surface of raw biochar enhanced its BET surface area (178.7 m2/g) and mesoporous volume ratio (42.1%). Moreover, the WBC-K-MnO2 nanocomposite exhibited the highest specific capacitance value of 234.3 F/g at a scan rate of 5 mV/s. The electrosorption isotherms and kinetic data were well explained by the Freundlich and pseudo-second order models, respectively. The WBC-K-MnO2 electrode demonstrated excellent reusability with a Pb2+ electrosorption efficiency of 76.3% after 15 cycles. Thus, the WBC-K-MnO2 nanocomposite can serve as a promising candidate for capacitive deionization of heavy metal contaminated water.

Urea functionalization of ultrasound-treated biochar: A feasible strategy for enhancing heavy metal adsorption capacity.

The main objective of a series of our researches is to develop a novel acoustic-based method for activation of biochar. This study investigates the capability of biochar in adsorbing Ni(II) as a hazardous contaminant and aims at enhancing its adsorption capacity by the addition of extra nitrogen and most probably phosphorous and oxygen containing sites using an ultrasono-chemical modification mechanism. To reach this objective, biochar physically modified by low-frequency ultrasound waves (USB) was chemically treated by phosphoric acid (H3PO4) and then functionalized by urea (CO(NH2)2). Cavitation induced by ultrasound waves exfoliates and breaks apart the regular shape of graphitic oxide layers of biochar, cleans smooth surfaces, and increases the porosity and permeability of biochar's carbonaceous structure. These phenomena synergistically combined with urea functionalization to attach the amine groups onto the biochar surface and remarkably increased the adsorption of Ni(II). It was found that the modified biochar could remove > 99% of 100 mg Ni(II)/L in only six hours, while the raw biochar removed only 73.5% of Ni(II) in twelve hours. It should be noted that physical treatment of biochar with ultrasound energy, which can be applied at room temperature for a very short duration, followed by chemical functionalization is an economical and efficient method of biochar modification compared with traditional methods, which are usually applied in a very severe temperature (>873 K) for a long duration. Such modified biochars can help protect human health from metal-ion corrosion of degrading piping in cities with aging infrastructure.

Chemical quality of bottled waters from three cities in eastern Alabama.

Twenty-five brands of bottled waters consisting of both purified and spring types collected randomly from three Alabama cities, USA were assessed for their suitability for human consumption. Water quality constituents analyzed include pH, conductivity, alkalinity, chloride, nitrate + nitrite, sulfate, phosphate, total carbon (TC), inorganic carbon (IC), total organic carbon (TOC), and 27 elements on the inductively coupled plasma-optical emission spectrometer (ICP-OES). The results obtained were compared with US EPA drinking water standards and the European union (EU) drinking water directive. Ni was non-detectable in all the samples and Cu, Pb, Sb, Zn, Mn, Al, Cr, Mg, P, Ca, sulfate, chloride and nitrates + nitrites were all below their respective USEPA drinking water standards or EU maximum admissible concentrations (MAC). The conductivity, pH, As, Cd, Hg, Zn, Se and Tl values in some samples exceeded the EU and USEPA standards for drinking water. No sample had pH > 8.5, but seven bottled water brands analyzed were acidic (pH < 6.5). Most of the sampled brands had TOC concentrations exceeding 3 mg/l. The concentrations of most water quality constituents analyzed, in most cases, were higher in the spring water brands compared to the purified or distilled brands of bottled water. A one-way parametric analysis of variance (ANOVA) conducted on pH, conductivity, IC, TOC, Ca, Na, K, Mg, Se, sulfate, chloride and nitrate + nitrite values for 10 brands of bottled water to ascertain the homogeneity of variances within and between the brands, suggested significant differences in variances across the brands at a 95% confidence level except for selenium, sodium and calcium.

Microbial stability evaluation of cement-based waste forms at different waste to cement ratio.

An evaluation of the effect of differences in chromium nitrate to cement ratio on the microbial stability of a chromium nitrate/cement waste form, as reflected in the leaching of chromium, calcium, magnesium and aluminum; was carried out in this study. An increase in the proportion of chromium in the waste form from 4.8 to 8.7% had no noticeable effect on microbial stability, with the total chromium leached essentially unchanged. Further increases in the proportion of chromium in the waste form from 8.7 to 10.7%, and from 10.7 to 15.9% resulted in a substantial decrease in microbial stability, with 3-fold and 1.3-fold increase in the total chromium leached, respectively, observed. For calcium, increases in the chromium proportion were accompanied with increases in the total calcium leached even though the increases were not in direct proportion to the increases in chromium proportion. For magnesium and aluminum, increases in the proportion of chromium within the range 4.8-10.7% were accompanied with increases in the total respective metals leached, with minor variation for each metal. On the whole, the maximum percentage chromium leached from the different waste forms was substantially lower than those of the other metals.

Evaluation of microbial stability of simulated solid and liquid waste forms using a refined biofilm formation method.

A refined biofilm formation method was used to evaluate the stability of a simulated liquid waste form containing a simulated liquid waste (salts) and cement in three different proportions, and a simulated solid waste form containing a simulated solid waste (resin) and cement in three different proportions. The experimental samples of all the simulated liquid waste forms showed evidence of microbial growth on them after 3 days of evaluation as indicated by substantial increase in sulfate production, and exhibited considerable instability to microbial degradation as indicated by substantial leaching of calcium. The experimental samples of all the simulated solid waste forms showed evidence of inhibition of growth of Thiobacillus thiooxidans for about 18 days, after which the growth of the microbe became evident in two out of three. Within the growth inhibition period, the differences between experimental and control samples were minor. After the growth of T. thiooxidans became evident, comparatively higher degradations were observed for the experimental samples of the resin containing solid waste forms.