Aluminum (Al) phytotoxicity is a major limitation in the production of crops in the soils with pH ≤ 5. Boron (B) is indispensable nutrient for the development of higher plants and B role has been reported in the alleviation Al toxicity. Trifoliate orange rootstock was grown in two B and two Al concentrations. The results of the present study showed that Al toxicity adversely inhibited root elongation and exhibited higher oxidative stress in terms of H2O2 and O2− under B-deficiency. Additionally, the X-ray diffraction (XRD) analysis confirmed the increase of the cellulose crystallinity in the cell wall (CW). Al-induced remarkable variations in the CW components were prominent in terms of alkali-soluble pectin, 2-keto-3-deoxyoctonic acid (KDO) and the degree of methyl-esterification (DME) of pectin. Interesting, B supply reduced the pectin (alkali-soluble) under Al toxicity. Moreover, the results of FTIR (Fourier transform infrared spectroscopy) and 13C-NMR (13C nuclear magnetic resonance) spectra revealed the decrease of carboxyl groups and cellulose by B application during Al exposure. Furthermore, B supply tended to decrease the Al uptake, CW thickness and callose formation. The study concluded that B could mitigate Al phytotoxicity by shielding potential Al binding sites and by reducing Al induced alterations in the CW cellulose and pectin components.

Knowledge of adsorption behavior of organic contaminants on high heat temperature treated biochars is essential for application of biochars as adsorbents in wastewater treatment and soil remediation. In this study, isotherms of 25 aromatic compounds adsorption on biochars pyrolyzed at 700 °C from biomass including wood chips, rice straw, bamboo chips, cellulose, lignin and chitin were investigated to establish correlations between adsorption behavior and physicochemical properties of biochars. Isotherms were well fitted by Polanyi theory-based Dubinin-Ashtakhov (DA) model with three parameters, i.e., adsorption capacity (Q⁰) and adsorption affinity (E and b). Besides the negative correlation of Q⁰ with molecular maximum cross-sectional areas (σ) of organic compounds, positive correlations of Q⁰ with total pore volume (Vₜₒₜₐₗ) and average diameter of micropore (D) of biochars were observed, indicating that adsorption by biochars is captured by the pore-filling mechanism with molecular sieving effect in biochar pores. Linear solvation energy relationships (LSERs) of adsorption affinity (E) with solvatochromic parameters of organic compounds (i. e., αₘ and π∗) were established, suggesting that hydrophobic effect, π-π interaction and hydrogen-bonding interaction are the main forces responsible for adsorption. The regression coefficient (π₁) and intercept (C) of obtained LSERs are correlated with biochar H/C and Rₘᵢcᵣₒ, respectively, implying that biochars with higher aromaticity and more micropores have stronger π-π bonding potential and hydrophobic effect potential with aromatic molecule, respectively. However, hydrogen-bonding potential of biochars for organic molecules is not changed significantly with properties of biochars. A negative correlation of b with biochar H/C is also obtained. These correlations could be used to predict the adsorption behavior of organic compounds on high heat temperature treated biochars from various biomass for the application of biochars as sorbents and for the estimating of environmental risks of organic compounds in the present of biochars.

Biochars are being increasingly applied in soil for carbon sequestration, fertility improvement, as well as contamination remediation. Phosphoric acid (H3PO4) pretreatment is a method for biochar modification, but the mechanism is not yet fully understood. In this work, biochars and the raw biomass were treated by H3PO4 prior to pyrolysis. Due to an acid catalysis and crosslink, the micropores of the pretreated particles were much more than those without H3PO4 pretreatment, resulting in the dramatical enhancement of specific surface areas of the pretreated particles. Crystalline cellulose (CL) exhibited a greater advantage in the formation of micropores than of amorphous lignin (LG) with H3PO4 modification. The formation mechanisms of micropores were: (a) H+ from H3PO4 contributes to micropores generation via H+ catalysis process; (b) the organic phosphate bridge protected the carbon skeleton from micropore collapse via the crosslinking of phosphate radical. The sorption capacities to carbamazepine (CBZ) and bisphenol A (BPA) increased after H3PO4 modification, which is ascribed to the large hydrophobic surface areas and more abundant micropores. Overall, H3PO4 pretreatment produced biochars with large surface area and high abundance of porous structures. Furthermore, the H3PO4 modified biochars can be applied as high adsorbing material as well as P-rich fertilizer.

The present study for the first time demonstrated the interactions of metal oxide (MO) nano-pollutants (CuO and Al2O3-NPs) with tissues and cellular DNA of tomato plants grown in soil sand: silt: clay (667:190:143) and Hoagland-hydroponic system and assessed the hazardous effects of NPs on cell physiology and biochemistry. Results of SEM equipped with EDX revealed attachment of variably shaped CuO-NPs (18 nm) and Al2O3-NPs (21 nm) on roots, and internalization followed by translocation in plants by ICP-MS and TEM. Significant variations in foliage surface area, chlorophyll, proteins, LPO, and antioxidant enzymes were recorded. Roots and shoots accumulated 225.8 ± 8.9 and 70.5 ± 4 μgAl g−1 DW, whereas Cu accumulation was 341.6 ± 14.3 (roots) and 146.9 ± 8.1 μg g−1 DW (shoots) which was significant (p ≤ 0.0005) as compared to control. The total soluble protein content in roots, shoots, and leaves collected from Al2O3-NPs treated plants increased by 120, 80, and 132%, respectively while in CuO-NPs treatments, the increase was 68 (roots), 36 (shoots), and 86% (leaves) over control. The level of antioxidant enzymes in plant tissues was significantly (p ≤ 0.05) higher at 2000 μg ml−1 of MONPs over control. A dose-dependent increase in reactive oxygen species (ROS), biphasic change of lower and higher fluorescence in mitochondria due to dissipation of mitochondrial membrane potential (ΔΨm) and membrane defects using propidium iodide were observed. Comparatively, CuO-NPs induced higher toxicity than Al2O3-NPs. Perceptible changes in proteins (amide-I & II), cellulose, glucose, galactose and other carbohydrates were observed under FT-IR. The binding studies with TmDNA showed fluorescence quenching of EtBr-TmDNA and acridine orange-TmDNA complex only by CuO-NPs with -ΔG and +ΔH and +ΔS values. However, Al2O3-NPs induced lesser change in TmDNA conformation. Conclusively, the results are novel in better demonstrating the mechanistic basis of nano-phyto-toxicity and are important which could be used to develop strategies for safe disposal of Al2O3-NPs and CuO-NPs.

Adsorption has been researched attempting to minimize the pollution caused by dyes, which represents a serious environmental problem as contamination of surface and ground water. Therefore, cellulose and its modified forms with amine and thiols groups constitute a class of versatile adsorbents for the removal of anionic dyes in aqueous solution. In this context, this work reports the preparation of cellulose modified by ethylene sulfide and ethylenediamine (Cel-ESEN), through the reaction of the cellulose modified by ethylene sulfide (CEL-ES) and ethylenediamine (EN). Materials were characterized by elemental analysis, which showed in the Cel-ESEN matrix 10.12 ± 0.10%, 5.52 ± 0.06% of sulfur and nitrogen, respectively. Nuclear magnetic resonance in the solid state of ¹³C (¹³C NMR) showed, for the Cel-ESEN matrix, a peak related to CH₂ groups from the molecules incorporated in the cellulose biopolymer. Crystalline Index obtained by X-ray diffraction (XRD) was in the order pure Cellulose > Cel-Cl > Cel-ES > Cel-ESEN. The adsorbent matrix (Cel-ESEN) was used in the removal of the remazol yellow GR (RY) dye in aqueous medium. Data obtained experimentally from kinetic study had the best adjustment to the proposed pseudo-second-order model. The adsorption process occurs in monolayer, is endothermic and thermodynamically favorable. Adsorption capacity of the modified material became 118 times higher than the starting material. These results suggest that the obtained biopolymer can be used as an alternative material to remove RY in aqueous solution.

Corncob is a kind of agricultural waste, mainly composed of cellulose and hemicellulose. In this study, anion adsorbent hyperbranched polyamide-modified corncob was synthesized by glutaraldehyde cross-linking, which has abundant terminal groups. Then, the effect of modification conditions for the adsorption of Cr (VI) onto modified material was studied. The structural characteristics and the functional properties of modified corncob (HPMC) were revealed by thermogravimetric analysis (TGA), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). Experimental results show that the optimum modification conditions were as follows: oxidized corncob 1 g, glutaraldehyde 2.5 mL, hyperbranched polyamide 10 mL, and a reaction time of 4 h under 60 °C. The effect of reaction temperature (factor C) on the removal rate of HPMC for Cr (VI) was the largest and GA dosage was the least. The equilibrium adsorption capacity of modified corncob for Cr (VI) was 47.8 mg/g (pH = 2, initial Cr (VI) concentration 100 mg/L, dosage 2 g/L, 4.0 h). The content of functional groups (-NH₂) on the surface of modified materials was obviously increased, the surface became rougher, and the thermal stability was improved. The adsorption mechanism was mainly electrostatic gravitation and oxidation-reduction reaction between HPMC and Cr (VI).

The dynamics of polycyclic aromatic hydrocarbon (PAH) degradation in Sphagnum litters and the decomposition of the litters were investigated. PAH concentration decreased to approximately half of the initial concentration as Sphagnum litters decayed. The initial PAH concentration was 489.2 ± 72.2 ng g⁻¹, and the concentration after 120 days of incubation was 233.0 ± 5.8 ng g⁻¹. The different PAH compositions changed concentrations at different times. The low-molecular-weight (LMW) and high-molecular-weight (HMW) PAHs started to be degraded after incubation and after 40 days of incubation, respectively. PAH concentrations in the Sphagnum litters correlated with the total organic carbon (TOC) content (p < 0.05), indicating that PAHs were associated with the TOC of the Sphagnum litters and were degraded as organic matter decayed. The positive relationship between LMW PAH concentration and the soluble carbohydrate content (p < 0.05) indicated that LMW PAHs and the readily decomposed organic carbon fractions were cometabolized, or that LMW PAHs were mainly absorbed by soluble carbohydrate. The weak negative correlation between fulvic acid (FA) and PAH concentrations (p < 0.1) indicated that FA may enhance PAH degradation. Redundancy analysis suggested that the contents of both soluble carbohydrate and cellulose significantly affected the changes in PAH concentrations (p < 0.05), and that FA content and C/N ratios may also contribute to the changes in PAH concentrations (p < 0.1). However, the polyphenol that was related to microbial activities was not associated with changes in PAH concentrations. These results suggested that litter quality is more important than microbial activities in PAH degradation in Sphagnum litters.

The work shown in this article demonstrate a novel example of converting olive industry solid waste (OISW) into a magnetic cellulose nanocrystalline (MNCs) to serve as selective magnetic sorbents for methylene blue. Olive industry solid waste contains about 40% cellulose. The cellulose was extracted in a powder form from olive industry solid waste by subjecting it to a multistep pulping and bleaching process. The extracted powder cellulose was then converted to nanocrystalline cellulose (NCs) by acid hydrolysis. The NCs were then treated with a solution of FeCl₃.6H₂O, FeSO₄, and H₂O by a colloidal suspension method which produced free-flowing porous MNCs. The produced MNCs are characterized by several spectroscopic and analytical techniques such as SEM, TEM, XRD, FTIR VSM, and TGA. The efficiency of the three polymers cellulose powder, NCs, and MNCs toward extracting methylene blue (MB) from water was evaluated. Cellulose powder and NCs showed acceptable tendency for methylene blue. However, MNCs showed excellent extraction efficiency toward MB. The thermodynamic studies revealed a spontaneous adsorption of MB by MNCs at various temperatures. The spontaneous adsorption could be attributed to the electrostatic interaction and H-bonding between MNCs and MB. However, the interaction between cellulose, NCs, and MB is limited to the H-bonding.

Soil organic matters (SOM) have a great retention effect on Cr(VI) migration in subsurface environment, which act as the main electron donors for Cr(VI) reduction; however, Cr(VI) reduction mechanism by different SOM fractions is still unclear, such as undissolved humic acid (HA) and humin (HM). In this study, HA and HM fractions extracted from typical black soil from Northeast China were used to investigate the reaction mechanism between humus functional groups and Cr(VI). According to the results, phenol and hydroxyl were determined as the main electron donors for Cr(VI) reduction by HA and HM instead of carboxyl and carbonyl, which were more likely involved in Cr complexation. Furthermore, Cr(VI) reduction was more dependent on aromatic carbon, rather than aliphatic carbon, and functional groups on the particle surfaces of HA and HM were much more active for Cr(VI) reduction than their interior part. Additionally, HM was found to have a relatively low Cr(VI) reduction capability compared with HA resulting from its high content of cellulose structures that are quite resistant to Cr(VI) oxidation. These results suggest that in the soil environment, undissolved HA tends to play a much more important role than HM in Cr(VI) reduction and retention in the condition that their mass contents are comparable.

Forward osmosis (FO) has emerged as a viable technology to alleviate the global water crisis. The greatest challenge facing the application of FO technology is the lack of an ideal draw solution with high water flux and low reverse salt flux. Hence, the objective of this study was to enhance FO by lowering reverse salt flux and maintaining high water flux; the method involved adding small concentrations of Al₂(SO₄)₃ to a MgCl₂ draw solution. Results showed that 0.5 M MgCl₂ mixed with 0.05 M of Al₂(SO₄)₃ at pH 6.5 achieved a lower reverse salt flux (0.53 gMH) than that of pure MgCl₂ (1.55 gMH) using an FO cellulose triacetate nonwoven (CTA-NW) membrane. This was due possibly to the flocculation of aluminum hydroxide in the mixed draw solution that constricted membrane pores, resulting in reduced salt diffusion. Moreover, average water fluxes of 4.09 and 1.74 L/m²-h (LMH) were achieved over 180 min, respectively, when brackish water (5 g/L) and sea water (35 g/L) were used as feed solutions. Furthermore, three types of membrane distillation (MD) membranes were selected for draw solution recovery; of these, a polytetrafluoroethylene membrane with a pore size of 0.45 μm proved to be the most effective in achieving a high salt rejection (99.90%) and high water flux (5.41 LMH) in a diluted draw solution.