In this work, the surface structures of biochars, derived from three types of biomass, switchgrass (SG), hardwood (HW) and softwood (SW) through either fast pyrolysis (FP) in a fluidized-bed reactor ...(at 500 °C) or slow pyrolysis (at 500° and 700 °C), were studied in detail, and compared with that of the activated carbons obtained by steam activation of the slow pyrolyzed biochars (at 500 °C). The surface acidic functional groups were determined quantitatively by the Boehm Titration method. The adsorptive properties of heavy metals, Zn2+ and Cu2+ onto the biochars and the activated carbons were investigated by the adsorption isotherms and SEM images, and correlated with the surface properties. ATR-FTIR and GC techniques were used to analyze the adsorptive behavior of phenol onto the biochars and activated carbons, and the results demonstrated that phenol adsorption capability is directly proportional to the micropore surface area as well as the combined level of the accessible carboxylic and lactonic groups. The relative adsorption capacity with respect to the biomass precursor follows the order: SW > HW > SG.
► pH 4.8 produced more favorable immobilization conditions for heavy metal. ► Phenol adsorbed onto fast pyrolysis biochar assumed a fast and irreversible process. ► Phenol adsorbed onto slow pyrolysis biochar was eliminated by heating and storage. ► Steam activation assumed a fast adsorption and desorption process for phenol.
Phosphorus-rich manure biochar has a potential for stabilizing Pb and other heavy metal contaminants, as well as serving as a sterile fertilizer. In this study, broiler litter biochars produced at ...350 and 650 °C were employed to understand how biochar’s elemental composition (P, K, Ca, Mg, Na, Cu, Pb, Sb, and Zn) affects the extent of heavy metal stabilization. Soil incubation experiments were conducted using a sandy, slightly acidic (pH 6.11) Pb-contaminated (19906 mg kg-1 total Pb primarily as PbCO3) small arms range (SAR) soil fraction (<250 μm) amended with 2-20 wt % biochar. The Pb stabilization in pH 4.9 acetate buffer reached maximum at lower (2–10 wt %) biochar amendment rate, and 350 °C biochar containing more soluble P was better able to stabilize Pb than the 650 °C biochar. The 350 °C biochar consistently released greater amounts of P, K, Mg, Na, and Ca than 650 °C biochar in both unbuffered (pH 4.5 sulfuric acid) and buffered (pH 4.9 acetate) systems, despite 1.9-4.5-fold greater total content of the 650 °C biochar. Biochars, however, did not influence the total extractable Pb over three consecutive equilibration periods consisting of (1) 1 week in pH 4.5 sulfuric acid (simulated leaching by rainfall), (2) 1 week in pH 4.9 acetate buffer (standard solution for toxicity characteristic leaching procedure), and (3) 1 h in pH 1.5 glycine at 37 °C (in vitro bioaccessibility procedure). Overall, lower pyrolysis temperature was favorable for stabilizing Pb (major risk driver of SAR soils) and releasing P, K, Ca, and other plant nutrients in a sandy acidic soil.
► Pecan shell activated carbon and broiler litter biochar enhanced copper sorption. ► Copper retention correlated with the equivalent release of proton, Ca, and Al. ► Biochar amendment is more ...effective in soil have lower heavy metal retention capacity.
The amendment of carbonaceous materials such as biochars and activated carbons is a promising
in situ remediation strategy for both organic and inorganic contaminants in soils and sediments. Mechanistic understandings in sorption of heavy metals on amended soil are necessary for appropriate selection and application of carbonaceous materials for heavy metal sequestration in specific soil types. In this study, copper sorption isotherms were obtained for soils having distinct characteristics: clay-rich, alkaline San Joaquin soil with significant heavy metal sorption capacity, and eroded, acidic Norfolk sandy loam soil having low capacity to retain copper. The amendment of acidic pecan shell-derived activated carbon and basic broiler litter biochar lead to a greater enhancement of copper sorption in Norfolk soil than in San Joaquin soil. In Norfolk soil, the amendment of acidic activated carbon enhanced copper sorption primarily via cation exchange mechanism, i.e., release of proton, calcium, and aluminum, while acid dissolution of aluminum cannot be ruled out. For San Joaquin soil, enhanced copper retention by biochar amendment likely resulted from the following additional mechanisms: electrostatic interactions between copper and negatively charged soil and biochar surfaces, sorption on mineral (ash) components, complexation of copper by surface functional groups and delocalized π electrons of carbonaceous materials, and precipitation. Influence of biochar on the release of additional elements (e.g., Al, Ca) must be carefully considered when used as a soil amendment to sequester heavy metals.
When direct flow velocity measurements are not feasible, the use of tracers can be a valuable tool. In the present study, both laboratory and field experiments were conducted to evaluate the ...applicability of quinine as a fluorescent tracer for estimating mean sheet flow velocities in different ambient light and surface morphology conditions. Quinine excels in low-light conditions when exposed to UVA light. This tracer was compared with dye and thermal tracers, all in liquid form. In these tracing techniques the tracers were injected into the flow, after which surface velocity was estimated by tracking the leading edge of the tracer plumes and applying a correction factor to calculate the mean velocity (in a water column). The visibility of the tracers was evaluated by measuring the relative luminance and contrast ratio of the quinine and dye tracer plumes. Results show that the quinine tracer can be used to estimate sheet flow velocities over a wide variety of soil and urban surfaces; it has better visibility in comparison to the dye tracer but, in some conditions, lower visibility than the thermal tracer. Although quinine is invisible under bright ambient light conditions, this tracer technique requires low-cost experimental setup and is useful in low-light conditions (e.g., night; twilight; shielded environments).
Biochars have received increasing attention in recent years because of a large-scale soil amendment to improve soil fertility, immobilize contaminants, and to serve as a recalcitrant carbon stock. ...Information is currently lacking in factors controlling the sorption capacity of manure-derived biochars. In this study, sorption isotherms for deisopropylatrazine, a stable metabolite of the widely applied herbicide atrazine, were obtained in acidic aqueous media (pH 5.5) for broiler litter-derived biochars formed by pyrolysis at 350 and 700 °C with and without steam activation at 800 °C. An increase in the Freundlich distribution coefficient (K(F)) and isotherm nonlinearity (n(F)) was observed with pyrolysis temperature and steam-activation, suggesting that the surface area and aromaticity (degree of carbonization) are the factors controlling the sorption capacity of chars at low surface coverage. At high surface coverage, the isotherms became increasingly linear, suggesting sorption on noncarbonized fraction of biochars. In binary-solute experiments, the sorption of deisopropylatrazine was significantly diminished by Cu(II), further suggesting the predominance of the surface adsorption mechanism at low surface coverage of biochars.
•DES are viable alternatives to Ionic Liquids in Desulfurization Processes.•DES present environmental and economic advantages in Desulfurization.•DES stability, recycling and disposal are crucial to ...Desulfurization market.•Urgent need to test the most promising DES in real matrices.
The impact of fossil fuels impurities on outdoor air pollution is today a matter of great concern, with the transportation sector playing a major role. Given global efforts to reduce sulfur oxides emissions, and the increasingly tighter legislations, removal of sulfur contaminants liquid highway fuels is a pressing issue worldwide. The purpose of this review is to provide a detailed state of the art review concerning the use of deep eutectic solvents (DES) in the removal of sulfur pollutants from transportation fuels. Furthermore, a comparative evaluation regarding the use of these solvents versus Ionic Liquids (ILs) is also provided, taking into account several aspects, such as, evolution of technologies, solvents composition, extraction efficiencies and environmental and economic considerations. The large gap in terms of efficiency of the reported technologies, either using ILs or DES, between simulated matrices and real fuels is also discussed, highlighting the importance of academia and industry hand in hand work.
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•ChCl:OA DES toxicity was, for the first time, evaluated in an anaerobic consortium.•DES concentration determines a beneficial or negative effect on biogas production.•Oxalic acid is ...the main responsible for the inhibitory effect.•The presence of choline chloride improved the production of biogas.
Deep eutectic solvents (DES), a new class of alternative solvents, have recently been used in the pre-treatment of lignocellulosic biomass. Due to the ability to dissolve phenolic compounds, they have been efficiently applied as delignification agents. However, to extend DES application to bioprocesses, such as Anaerobic Digestion (AD), their toxicity to microbial consortia must be evaluated. In this work, an effective delignifying DES, composed of choline chloride (ChCl) and oxalic acid (OA) (1:1) was prepared and its effect evaluated, for the first time, in biogas production. Results show that the presence of DES had both beneficial and detrimental effects on the anaerobic consortium, depending on its concentration. In the concentration range of 0.3–12.5 g/L, the presence of DES led to a lag-phase of 1 to 8 d as the DES concentration increased. However, after the lag-phase has been surpassed, DES up to a concentration of 12.5 g/L improved the biogas production, reaching an accumulated biogas volume three times higher than the control assay for the concentration of 12.5 g/L. For the highest DES concentrations (19.8–78.1 g/L), the biogas production was inhibited. The assays performed with DES components alone have indicated that OA at 3.2 g/L was the main responsible for the inhibition of biogas production (50% less biogas produced than the control). ChCl at 4.9 g/L has not presented a lag-phase and produced an accumulated biogas volume like the control assay (1200 mL for 30 d incubation). This work points out that ChCl:OA DES may be used in the delignification of biomass further submitted to AD, provided the inhibitory concentrations of OA are not achieved.
Precipitation extremes in mainland Portugal (south-western Europe) using daily precipitation data recorded in the period 1941–2007 (67 years) at 57 meteorological stations scattered across the area ...are studied at an annual scale. Trends in selected precipitation annual indices that are calculated from these data are investigated, in particular trends in the intensity, frequency and duration of extreme precipitation events. Special attention is dedicated to local and regional variability. The spatial correlations between the annual trends in mean precipitation and in the extremes are analysed. Moreover, the relationships between the variability of the North Atlantic Oscillation (NAO) index and several indices related to the frequency and intensity of the precipitation at the 57 stations were also investigated. Results show that several stations have predominantly negative tendencies in the precipitation indices, although the majority of stations did not show statistically significant change over time in the 1941–2007 period. At the regional level, the decreasing trend in the simple daily precipitation intensity index is the only one statistically significant at the 5 % level and appears to be related to the predominance of the positive phase of the NAO. For the period 1976–2007, the proportion of the total precipitation attributed to heavy and very heavy precipitation events increased and, consequently, daily precipitation events show a tendency to become more intense. Moreover, correlation analysis show that the most extreme events could be changing at a faster absolute rate in relation to the mean than more moderate events.
Accurate measurement of shallow flows is important for hydraulics, hydrology and water resources management. The objective of this paper is to discuss a technique for shallow flow and overland flow ...velocity estimation that uses infrared thermography. Laboratory flumes and different bare, vegetated and paved field surfaces were used to test the technique. Results show that shallow flow surface velocities estimated using thermal tracers and infrared technology are similar to estimates obtained using the Acoustic Doppler Velocimeter; similar results were also obtained for overland flow velocity estimates using thermography, here comparing with the dye tracer technique. The thermographic approach revealed some potential as a flow visualization technique, and leaves space for future studies and research.
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