Liuyan Yang

Biochar derived from anaerobically digested sugar beet tailings: Characterization and phosphate removal potential

Two biochars were produced from anaerobically digested and undigested sugar beet tailings through slow-pyrolysis at 600°C. The digested sugar beet tailing biochar (DSTC) and raw sugar beet tailing biochar (STC) yields were around 45.5% and 36.3% of initial dry weight, respectively. Compared to STC, DSTC had similar pH and surface functional groups, but higher surface area, and its surface was less negatively charged. SEM-EDS and XRD analyses showed that colloidal and nano-sized periclase (MgO) was presented on the surface of DSTC. Laboratory adsorption experiments were conducted to assess the phosphate removal ability of the two biochars, an activated carbon (AC), and three Fe-modified biochar/AC adsorbents. The DSTC showed the highest phosphate removal ability with a removal rate around 73%. Our results suggest that anaerobically digested sugar beet tailings can be used as feedstock materials to produce high quality biochars, which could be used as adsorbents to reclaim phosphate.

Removal of phosphate from aqueous solution by biochar derived from anaerobically digested sugar beet tailings.

Biochar converted from agricultural residues or other carbon-rich wastes may provide new methods and materials for environmental management, particularly with respect to carbon sequestration and contaminant remediation. In this study, laboratory experiments were conducted to investigate the removal of phosphate from aqueous solution by biochar derived from anaerobically digested sugar beet tailings (DSTC). Batch adsorption kinetic and equilibrium isotherm experiments and post-adsorption characterizations using SEM-EDS, XRD, and FTIR suggested that colloidal and nano-sized MgO (periclase) particles on the biochar surface were the main adsorption sites for aqueous phosphate. Batch adsorption experiments also showed that both initial solution pH and coexisting anions could affect the adsorption of phosphate onto the DSTC biochar. Of the mathematical models used to describe the adsorption kinetics of phosphate removal by the biochar, the Ritchie N_th-order (N=1.14) model showed the best fit. Two heterogeneous isotherm models (Freundlich and Langmuir-Freundlich) fitted the experimental isotherm of phosphate adsorption onto the biochar better than the Langmuir adsorption model. Our results suggest that biochar converted from anaerobically digested sugar beet tailings is a promising alternative adsorbent, which can be used to reclaim phosphate from water or reduce phosphate leaching from fertilized soils. In addition, there is no need to regenerate the exhausted biochar because the phosphate-laden biochar contains abundance of valuable nutrients, which may be used as a slow-release fertilizer to enhance soil fertility and to sequester carbon.

Adsorption of sulfamethoxazole on biochar and its impact on reclaimed water irrigation

Reclaimed water irrigation can satisfy increasing water demand, but it may also introduce pharmaceutical contaminants into the soil and groundwater environment. In this work, a range of laboratory experiments were conducted to test whether biochar can be amended in soils to enhance removal of sulfamethoxazole (SMX) from reclaimed water. Eight types of biochar were tested in laboratory sorption experiments yielding solid-water distribution coefficients (K(d)) of 2-104 L/kg. Two types of biochar with relatively high K(d) were used in column leaching experiments to assess their effect on reclaimed water SMX transport through soils. Only about 2-14% of the SMX was transported through biochar-amended soils, while 60% was found in the leachate of the unamended soils. Toxicity characteristic leaching experiments confirmed that the mobility and bioavailability of SMX in biochar-amended soils were lower than that of unamended soils. However, biochar with high accumulations of SMX was still found to inhibit the growth of the bacteria compared to biochar with less SMX which showed no effects. Thus, biochar with very high pharmaceutical sorption abilities may find use as a low-cost alternative sorbent for treating wastewater plant effluent, but should be used with caution as an amendment to soils irrigated with reclaimed water or waste water.

Engineered carbon (biochar) prepared by direct pyrolysis of Mg-accumulated tomato tissues: Characterization and phosphate removal potential

An innovative method was developed to produce engineered biochar from magnesium (Mg) enriched tomato tissues through slow pyrolysis in a N2 environment. Tomato plants treated with 25mM Mg accumulated much higher level of Mg in tissue, indicating Mg can be substantially enriched in tomato plants, and pyrolysis process further concentrated Mg in the engineered biochar (8.8% Mg). The resulting Mg-biochar composites (MgEC) showed better sorption ability to phosphate (P) in aqueous solutions compared to the other four tomato leaves biochars. Statistical analysis showed a strong and significant correlation between P removal rate and biochar Mg content (R(2)=0.78, and p<0.001), indicating the enriched Mg in the engineered biochar is the main factor controlling its P removal ability. SEM-EDX, XRD and XPS analyses showed that nanoscale Mg(OH)2 and MgO particles were presented on the surface of MgEC, which serve as the main adsorption sites for aqueous P.

Deposition and transport of functionalized carbon nanotubes in water-saturated sand columns

Knowledge of the fate and transport of functionalized carbon nanotubes (CNTs) in porous media is crucial to understand their environmental impacts. In this study, laboratory column and modeling experiments were conducted to mechanistically compare the retention and transport of two types of functionalized CNTs (i.e., single-walled nanotubes and multi-walled nanotubes) in acid-cleaned, baked, and natural sand under unfavorable conditions. The CNTs were highly mobile in the acid-cleaned sand columns but showed little transport in the both natural and baked sand columns. In addition, the retention of the CNTs in the both baked and natural sand was strong and almost irreversible even after reverse, high-velocity, or surfactant flow flushing. Both experimental and modeling results showed that pH is one of the factors dominating CNT retention and transport in natural and baked sand. Retention of the functionalized CNTs in the natural and baked sand columns reduced dramatically when the system pH increased. Our results suggest that the retention and transport of the functionalized CNTs in natural sand porous media were mainly controlled by strong surface deposition through the electrostatic and/or hydrogen-bonding attractions between surface function groups of the CNTs and metal oxyhydroxide impurities on the sand surfaces.

Combination of two-dimensional correlation spectroscopy and parallel factor analysis to characterize the binding of heavy metals with DOM in lake sediments

Enhanced knowledge on the binding of heavy metal (HM) with dissolved organic matter (DOM) is essential for understanding the toxicity and migration of HMs. In this study, two-dimensional correlation spectroscopy (2D-COS) and parallel factor (PARAFAC) analysis were combined to characterize the metal binding properties of DOMs, which were respectively extracted from macrophyte- and algal-dominant sediments (named MDOM and ADOM) in a eutrophic shallow lake. 2D absorption COS revealed that MDOM exhibited more HM binding sites (193, 195, 196, 199, 201, 203, 205, 207, 208, 212, 217 nm) than ADOM (201, 205 nm). PARAFAC analysis identified one protein- and two humic-like components from all titrated samples, with each component exhibiting different binding behaviors. The modified Stern-Volmer model showed that PARAFAC-derived components in MDOM had higher conditional stability constants (logKM) than in ADOM, suggesting that macrophyte-dominant sediments might play a more important role in the detoxification of HMs. Meanwhile, low binding abilities of Zn(II)-DOM complexes indicated that the toxicity of zinc in eutrophic lakes should not be overlooked. More aromatic functional groups and binding sites were suggested to be responsible for the high binding ability. 2D-COS was a better approach than PARAFAC analysis for exploring HM-DOM interaction.

Time-dependent oxidative stress and histopathological changes in Cyprinus carpio L. exposed to microcystin-LR

Microcystins (MCs) are produced by cyanobacteria in aquatic environments and are a potential risk to aquatic organisms. Increasing evidence suggests that oxidative stress may play an important role in the toxicity mechanism of MCs on fish, but most studies were based on relatively high concentrations. In this study, the effect of time-dependent oxidative stress in livers of Cyprinus carpio L. (C. carpio) exposed to 10xa0μgxa0l−1 of microcystin-LR (MC-LR) for 0–14xa0days was investigated. MC-LR induced histopathological changes in liver and gills were also assessed after 14xa0days exposure. Electron paramagnetic resonance (EPR) spectrum was used to directly investigate the reactive oxygen species (ROS) in fish liver and results showed that hydroxyl radical (∙OH) was significantly induced at 0.5xa0day and then tended to decline with an increase of exposure period. As a response of antioxidant, catalase (CAT) activity increased slightly at first and then decreased with exposure period. A pronounced promotion of glutathione-S-transferase (GST) indicated that the conjugation reaction of MC-LR and GSH occurred. A time-dependent decrease of reduced glutathione (GSH) with an increase of oxidized glutathione (GSSG) level suggested GSH was involved in detoxification of MC-LR in the liver. Oxidative damage was evidenced by the significant increase of malondialdehyde (MDA) level at 2–6xa0days. After 14xa0days exposure, a series of pathological changes, like partially dissolved parenchymal architecture, vacuolar degeneration, necrosis, hemorrhage and slight inflammatory cells infiltration in fish liver tissues could be observed. Scanning electron microscopic (SEM) studies showed that dissolved MC-LR could also result in pathological changes like partial broken epithelial cells, deformed taste buds and loose gill filament and lamella in gill tissues. These results suggest that although a restoring response occurred, C. carpio could still be adversely affected by MC-LR at 10xa0μgxa0l−1.

Synthesis of a multifunctional graphene–carbon nanotube aerogel and its strong adsorption of lead from aqueous solution

Mechanically enhanced aerogels of graphene sheets and carbon nanotubes (CNTs) were prepared via hydrothermal reduction of graphene oxide and CNTs in the presence of ferrous ions (FeSO4 solution). The resultant graphene–CNT aerogels possess a 3-D network of carbon structures containing micro-sized pores and α-FeOOH nanorods within the matrix. The CNTs may act as a scaffold in the aerogels to resist compressive stress and prevent them from collapse. The aerogels have very low density (0.011–0.087 g cm−3), depending on the amount of ferrous ions used in the synthesis. In addition, the aerogels also have excellent mechanical properties with elastic modulus between 0.011 and 0.29 MPa. Because of their porous structures, the graphene–CNTs aerogels showed excellent removal ability to aqueous lead with rates between 230 and 451 mg g−1 and thus could be potentially used as a promising adsorbent for many environmental applications.

Microcystin-LR induced oxidative stress and ultrastructural alterations in mesophyll cells of submerged macrophyte Vallisneria natans (Lour.) Hara.

Microcystins produced by cyanobacteria in the aquatic environment are a potential risk to aquatic plants. In the present study, the uptake of microcystin-LR (MC-LR) and related physiological and biochemical effects on Vallisneria natans (Lour.) Hara were investigated at concentrations of 0.1-25.0 μg L(-1). Results showed that O(2)(-) intensity was significantly induced at 1.0 μg L(-1) and reached a maximum level at 5.0 μg L(-1). Superoxide dismutase (SOD) and peroxidase (POD) were induced with increasing MC-LR concentrations as an antioxidant response. Catalase (CAT) was significantly induced while GSH/GSSG (reduced/oxidized glutathione) ratio was significantly reduced at 0.1 μg L(-1). The induction of glutathione S-transferase (GST) and inhibition of GSH revealed that GSH was involved in the detoxification of MC-LR in plants. Oxidative damage was evidenced by the significant increase of malondialdehyde content at 1.0 μg L(-1). A pigment pattern change and a series of significant ultrastructural alterations were also observed due to MC-LR exposure. The lowest non-effect concentration of MC-LR for V. natans at the subcellular and molecular level is around 0.5 μg L(-1). These results imply that even at relatively low MC-LR concentrations the aquatic plants may still suffer a negative ecological impact.

Bioaccumulation, oxidative stress and HSP70 expression in Cyprinus carpio L. exposed to microcystin-LR under laboratory conditions.

Microcystin-LR (MC-LR) produced by cyanobacteria are potent specific hepatotoxins. So far the pathogenesis of environmental MC-LR toxicity to aquatic organisms has not been fully elucidated. In the present study the accumulation of MC-LR was investigated in various organs/tissues of Cyprinus carpio L. (C. carpio) following exposure to MC-LR for 14 d at environmentally relevant concentrations (0.1 to 10 μg L(-1)). Results showed that the presence of MC-LR enhanced toxin accumulation in all investigated organs and the highest accumulation was found in the liver of fish exposed to 5.0 μg L(-1) of MC-LR. An EPR analysis indicated ·OH intensity in liver was significantly induced at 0.1 μg L(-1) of MC-LR and then restored when the MC-LR concentration was greater than 0.1 μg L(-1). After 14-day exposure, MC-LR (1.0-10.0 μg L(-1) of MC-LR) caused a pronounced promotion of glutathione S-transferase (GST) activity and a depletion of reduced glutathione (GSH) content in fish liver, which indicated that GSH was involved in detoxification of MC-LR and the conjugation reaction of MC-LR and GSH occurred. A mild oxidative damage was evidenced by the accumulation of malondialdehyde (MDA) level at 5.0 μg L(-1) of MC-LR exposure, but which was restored when the MC-LR concentration was increased to 10.0 μg L(-1). The responses of antioxidant enzymes and the induction of HSP70 expression might contribute to MC-LR tolerance of C. carpio. However, the protein phosphatase (PP) activities were strikingly inhibited in all treated groups. Thus, the overall toxicity of environmental MC-LR on C. carpio seems to be initiated in the liver via both the ROS pathway and the PP inhibition pathway, and the latter might be more important when ambient MC-LR concentration is greater than 0.1 μg L(-1). More importantly, these results can help to support the evaluation on the potential effects of MC-LR under common environmental concentrations.