Season S. Chen

Engineered/designer biochar for contaminant removal/immobilization from soil and water: Potential and implication of biochar modification

The use of biochar has been suggested as a means of remediating contaminated soil and water. The practical applications of conventional biochar for contaminant immobilization and removal however need further improvements. Hence, recent attention has focused on modification of biochar with novel structures and surface properties in order to improve its remediation efficacy and environmental benefits. Engineered/designer biochars are commonly used terms to indicate application-oriented, outcome-based biochar modification or synthesis. In recent years, biochar modifications involving various methods such as, acid treatment, base treatment, amination, surfactant modification, impregnation of mineral sorbents, steam activation and magnetic modification have been widely studied. This review summarizes and evaluates biochar modification methods, corresponding mechanisms, and their benefits for contaminant management in soil and water. Applicability and performance of modification methods depend on the type of contaminants (i.e., inorganic/organic, anionic/cationic, hydrophilic/hydrophobic, polar/non-polar), environmental conditions, remediation goals, and land use purpose. In general, modification to produce engineered/designer biochar is likely to enhance the sorption capacity of biochar and its potential applications for environmental remediation.

A critical review on sustainable biochar system through gasification: Energy and environmental applications

This review lays great emphasis on production and characteristics of biochar through gasification. Specifically, the physicochemical properties and yield of biochar through the diverse gasification conditions associated with various types of biomass were extensively evaluated. In addition, potential application scenarios of biochar through gasification were explored and their environmental implications were discussed. To qualitatively evaluate biochar sustainability through the gasification process, all gasification products (i.e., syngas and biochar) were evaluated via life cycle assessment (LCA). A concept of balancing syngas and biochar production for an economically and environmentally feasible gasification system was proposed and relevant challenges and solutions were suggested in this review.

Valorization of food waste into hydroxymethylfurfural: Dual role of metal ions in successive conversion steps.

This study aimed to transform food waste into a value-added chemical, hydroxymethylfurfural (HMF), and unravel the tangled effects induced by the metal catalysts on each single step of the successive conversion pathway. The results showed that using cooked rice and bread crust as surrogates of starch-rich food waste, yields of 8.1-9.5% HMF and 44.2-64.8% glucose were achieved over SnCl4 catalyst. Protons released from metal hydrolysis and acidic by-products rendered Brønsted acidity to catalyze fructose dehydration and hydrolysis of glycosidic bond. Lewis acid site of metals could facilitate both fructose dehydration and glucose isomerization via promoting the rate-limiting internal hydride shift, with the catalytic activity determined by its electronegativity, electron configuration, and charge density. Lewis acid site of a higher valence also enhanced hydrolysis of polysaccharide. However, the metals also catalyzed undesirable polymerization possibly by polarizing the carbonyl groups of sugars and derivatives, which should be minimized by process optimization.

Catalytic valorization of starch-rich food waste into hydroxymethylfurfural (HMF): Controlling relative kinetics for high productivity

This study aimed to maximize the valorization of bread waste, a typical food waste stream, into hydroxymethylfurfural (HMF) by improving our kinetic understanding. The highest HMF yield (30mol%) was achieved using SnCl4 as catalyst, which offered strong derived Brønsted acidity and moderate Lewis acidity. We evaluated the kinetic balance between these acidities to facilitate faster desirable reactions (i.e., hydrolysis, isomerization, and dehydration) relative to undesirable reactions (i.e., rehydration and polymerization). Such catalyst selectivity of SnCl4, AlCl3, and FeCl3 was critical in maximizing HMF yield. Higher temperature made marginal advancement by accelerating the undesirable reactions to a similar extent as the desirable pathways. The polymerization-induced metal-impregnated high-porosity carbon was a possible precursor of biochar-based catalyst, further driving up the economic potential. Preliminary economic analysis indicated a net gain of USD 43-236 per kilogram bread waste considering the thermochemical-conversion cost and chemical-trading revenue.

Potential impact of flowback water from hydraulic fracturing on agricultural soil quality: metal/metalloid bioaccessibility, Microtox bioassay, and enzyme activities

Hydraulic fracturing has advanced the development of shale gas extraction, while inadvertent spills of flowback water may pose a risk to the surrounding environment due to its high salt content, metals/metalloids (As, Se, Fe and Sr), and organic additives. This study investigated the potential impact of flowback water on four representative soils from shale gas regions in Northeast China using synthetic flowback solutions. The compositions of the solutions were representative of flowback water arising at different stages after fracturing well establishment. The effects of solution composition of flowback water on soil ecosystem were assessed in terms of metal mobility and bioaccessibility, as well as biological endpoints using Microtox bioassay (Vibrio fischeri) and enzyme activity tests. After one-month artificial aging of the soils with various flowback solutions, the mobility and bioaccessibility of As(V) and Se(VI) decreased as the ionic strength of the flowback solutions increased. The results inferred a stronger binding affinity of As(V) and Se(VI) with the soils. Nevertheless, the soil toxicity to Vibrio fischeri only presented a moderate increase after aging, while dehydrogenase and phosphomonoesterase activities were significantly suppressed with increasing ionic strength of flowback solutions. On the contrary, polyacrylamide in the flowback solutions led to higher dehydrogenase activity. These results indicated that soil enzyme activities were sensitive to the composition of flowback solutions. A preliminary human health risk assessment related to As(V) suggested a low level of cancer risk through exposure via ingestion, while holistic assessment of environmental implications is required.

Polar aprotic solvent-water mixture as the medium for catalytic production of hydroxymethylfurfural (HMF) from bread waste

Valorisation of bread waste for hydroxymethylfurfural (HMF) synthesis was examined in dimethyl sulfoxide (DMSO)-, tetrahydrofuran (THF)-, acetonitrile (ACN)-, and acetone-water (1:1v/v), under heating at 140°C with SnCl4 as the catalyst. The overall rate of the process was the fastest in ACN/H2O and acetone/H2O, followed by DMSO/H2O and THF/H2O due to the rate-limiting glucose isomerisation. However, the formation of levulinic acid (via rehydration) and humins (via polymerisation) was more significant in ACN/H2O and acetone/H2O. The constant HMF maxima (26-27mol%) in ACN/H2O, acetone/H2O, and DMSO/H2O indicated that the rates of desirable reactions (starch hydrolysis, glucose isomerisation, and fructose dehydration) relative to undesirable pathways (HMF rehydration and polymerisation) were comparable among these mediums. They also demonstrated higher selectivity towards HMF production over the side reactions than THF/H2O. This study differentiated the effects of polar aprotic solvent-water mediums on simultaneous pathways during biomass conversion.

Valorization of Lignocellulosic Fibres of Paper Waste into Levulinic Acid using Solid and Aqueous Brønsted Acid

This study aims to produce levulinic acid (LA) from paper towel waste in environment-friendly and economically feasible conditions, and evaluate the difference using solid and aqueous Brønsted acids. Direct dehydration of glucose to LA required sufficiently strong Brønsted acidity, where Amberlyst 36 demonstrated rapid production of approximately 30Cmol% of LA in 20min. However, the maximum yield of LA was limited by mass transfer. In contrast, the yield of LA gradually increased to over 40Cmol% in 1M H2SO4 at 150°C in 60min. The SEM images revealed the conversion in dilute acids under microwave at 150°C resulting in swelling structures of cellulose, which were similar to the pre-treatment process with concentrated acids. Further increase in reaction temperature to 200°C significantly shortened the reaction time from 60 to 2.5min, which saved the energy cost as revealed in preliminary cost analysis.

Production of 5-hydroxymethylfurfural from starch-rich food waste catalyzed by sulfonated biochar

Sulfonated biochar derived from forestry wood waste was employed for the catalytic conversion of starch-rich food waste (e.g., bread) into 5-hydroxymethylfurfural (HMF). Chemical and physical properties of catalyst were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and elemental analysis. The conversion of HMF was investigated via controlling the reaction parameters such as catalyst loading, temperature, and reaction time. Under the optimum reaction conditions the HMF yield of 30.4 Cmol% (i.e., 22 wt% of bread waste) was achieved in the mixture of dimethylsulfoxide (DMSO)/deionized-water (DIW) at 180 °C in 20 min. The effectiveness of sulfonated biochar catalyst was positively correlated to the density of strong/weak Brønsted acidity (SO3H, COOH, and OH groups) and inversely correlated to humins content on the surface. With regeneration process, sulfonated biochar catalyst displayed excellent recyclability for comparable HMF yield from bread waste over five cycles.

Insights into the subsurface transport of As(V) and Se(VI) in produced water from hydraulic fracturing using soil samples from Qingshankou Formation, Songliao Basin, China

Produced water is a type of wastewater generated from hydraulic fracturing, which may pose a risk to the environment and humans due to its high ionic strength and the presence of elevated concentrations of metals/metalloids that exceed maximum contamination levels. The mobilization of As(V) and Se(VI) in produced water and selected soils from Qingshankou Formation in the Songliao Basin in China were investigated using column experiments and synthetic produced water whose quality was representative of waters arising at different times after well creation. Temporal effects of produced water on metal/metalloid transport and sorption/desorption were investigated by using HYDRUS-1D transport modelling. Rapid breakthrough and long tailings of As(V) and Se(VI) transport were observed in Day 1 and Day 14 solutions, but were reduced in Day 90 solution probably due to the elevated ionic strength. The influence of produced water on the hydrogeological conditions (i.e., change between equilibrium and non-equilibrium transport) was evidenced by the change of tracer breakthrough curves before and after the leaching of produced water. This possibly resulted from the sorption of polyacrylamide (PAM (-CH2CHCONH2-)n) onto soil surfaces, through its use as a friction reducer in fracturing solutions. The sorption was found to be reversible in this study. Minimal amounts of sorbed As(V) were desorbed whereas the majority of sorbed Se(VI) was readily leached out, to an extent which varied with the composition of the produced water. These results showed that the mobilization of As(V) and Se(VI) in soil largely depended on the solution pH and ionic strength. Understanding the differences in metal/metalloid transport in produced water is important for proper risk management.

Aging effects on chemical transformation and metal(loid) removal by entrapped nanoscale zero-valent iron for hydraulic fracturing wastewater treatment

In this study, alginate and polyvinyl alcohol (PVA)-alginate entrapped nanoscale zero-valent iron (nZVI) was tested for structural evolution, chemical transformation, and metals/metalloids removal (Cu(II), Cr(VI), Zn(II), and As(V)) after 1-2month passivation in model saline wastewaters from hydraulic fracturing. X-ray diffraction analysis confirmed successful prevention of Fe0 corrosion by polymeric entrapment. Increasing ionic strength (I) from 0 to 4.10M (deionized water to Day-90 fracturing wastewater (FWW)) with prolonged aging time induced chemical instability of alginate due to dissociation of carboxyl groups and competition for hydrogen bonding with nZVI, which caused high Na (7.17%) and total organic carbon (24.6%) dissolution from PVA-alginate entrapped nZVI after 2-month immersion in Day-90 FWW. Compared to freshly-made beads, 2-month aging of PVA-alginate entrapped nZVI in Day-90 FWW promoted Cu(II) and Cr(VI) uptake in terms of the highest removal efficiency (84.2% and 70.8%), pseudo-second-order surface area-normalized rate coefficient ksa (2.09×10-1Lm-2h-1 and 1.84×10-1Lm-2h-1), and Fe dissolution after 8-h reaction (13.9% and 8.45%). However, the same conditions inhibited Zn(II) and As(V) sequestration in terms of the lowest removal efficiency (31.2% and 39.8%) by PVA-alginate nZVI and ksa (4.74×10-2Lm-2h-1 and 6.15×10-2Lm-2h-1) by alginate nZVI. The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in metals/metalloids removal by entrapped nZVI after aging was attributed to distinctive removal mechanisms: (i) enhanced Cu(II) and Cr(VI) removal by nZVI reduction with accelerated electron transfer after pronounced dissolution of non-conductive polymeric immobilization matrix; (ii) suppressed Zn(II) and As(V) removal by nZVI adsorption due to restrained mass transfer after blockage of surface-active micropores. Entrapped nZVI was chemically fragile and should be properly stored and regularly replaced for good performance.