This study developed a novel Hg(II) immobilization strategy by firstly incubating algal cells in high-phosphate cultures for surface modification, followed by obtaining the P-rich biomass as adsorbents for enhanced Hg(II) removal and then charring the Hg-loaded biomass to prevent leaching of phosphate and to immobilize Hg(II). For algal surface modification, Scenedesmus obtusus XJ-15 were cultivated under different P concentrations and obtained the highest sites concentration of surface phosphoryl functional groups in 80 mg L⁻¹ P cultures. For Hg(II) adsorption, biomass from 80 mg L⁻¹ P cultures (B-80) achieved the highest saturated sorption capacity of 95 mg g⁻¹ fitting to Langmuir isotherm model under the optimum pH of 5.0. For charring stabilization, the Hg-loaded B-80 was calcinated under different temperatures, and the product obtained from 300 °C charring showed the lowest Hg(II) leaching rate without P release. Moreover, FT-IR and XPS analysis indicate that the surge of surface phosphoryl functional groups dominated the enhancement of Hg(II) sorption and also Hg(II) charring immobilization. The above results suggested that the developed strategy is promising for both phosphate and mercury removal from water and for co-immobilization of P and Hg(II) to prevent leaching.

Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

Groundwater with elevated As concentrations is a global concern, and low-cost, high-efficiency removal technologies are necessary. Therefore, we have prepared three adsorbent FeMnLa-impregnated biochar composites (FMLBCs) for the efficient removal of As(III) from aqueous solutions and characterized them using a variety of techniques. We found that the efficiency of As(III) removal increased with increasing La content and that the removal mainly occurred via adsorption and oxidation. Moreover, the removal of As(III) by FMLBCs was rapid and was best fitted to a pseudo-second-order kinetic model. The adsorption isotherms were well described by the Langmuir equation, and the maximum As(III) adsorption capacity was 15.34 mg g⁻¹. These results highlight the significant potential of FMLBCs as adsorbents for As(III) removal from aqueous solutions.

A new carboxylate-functionalized hydrochar (CFHC) was successfully prepared by reaction of hydrochar with maleic anhydride under solvent-free conditions and followed by deprotonating carboxyl group of hydrochar with NaHCO₃ solution. CFHC was characterized using X-ray photoelectron spectroscopy (XPS), elemental analysis (EA), zeta potential, Brunauer-Emmett-Teller surface area (BET) and Fourier-transform infrared spectroscopy (FTIR), and its adsorption properties and mechanisms to methylene blue (MB) and Cd(II) were investigated using the batch method. The isotherm adsorption data were accorded with Langmuir model and the maximum uptakes were 1155.57 and 90.99 mg/g for MB and Cd(II) at the temperature of 303 K, respectively. The joint analysis of batch experiments and characterizations of hydrochar confirmed the π-π interaction was accompanied by electrostatic interaction and hydrogen bond for MB adsorption, while the surface complexation and ion exchange were predominant mechanisms for Cd(II) adsorption. Therefore, a highly effective adsorbent CFHC prepared by a simple and environmentally friendly solid-phase synthesis is a promising candidate for wastewater treatment.

In this study, carbon nanotube-based adsorbents, oxidized multi-walled carbon nanotube (OMWCNT) with non-magnetic property and OMWCNT-Fe₃O₄ and OMWCNT-κ-carrageenan-Fe₃O₄ nanocomposites with magnetic property, having different structural and surface properties were prepared and their adsorptive properties for the removal of toxic diquat dibromide (DQ) herbicide from water by adsorption were determined in detail. For each adsorption system, the effects of initial DQ concentration, contact time and temperature on the adsorption processes were determined. Equilibrium time was found to be 300 min for DQ solutions. OMWCNT showed faster adsorption and higher maximum adsorption capacity value than magnetic adsorbents. With increasing initial herbicide concentration from 5.43 mg.L⁻¹ to 16.3 mg.L⁻¹, the values of initial sorption rate exhibited a decrease from 29.1 mg.g⁻¹.min⁻¹ to 4.28 mg.g⁻¹.min⁻¹ for OMWCNT-DQ system, from 1.21 mg.g⁻¹.min⁻¹ to 0.823 mg.g⁻¹.min⁻¹ for OMWCNT-Fe₃O₄-DQ system and from 0.674 mg.g⁻¹.min⁻¹ to 0.612 mg.g⁻¹.min⁻¹ OMWCNT-κ-carrageenan-Fe₃O₄ system. Maximum adsorption capacity value of OMWCNT was approximately 2.8-fold higher than magnetic OMWCNT-Fe₃O₄ and 5.4-fold higher than magnetic OMWCNT-κ-carrageenan-Fe₃O₄ at 25 °C. Adsorption kinetic and isotherm data obtained for all adsorption systems were well-fitted by pseudo second-order and Langmuir models, respectively. Thermodynamic parameters indicated that the adsorption of DQ onto carbon nanotube-based adsorbents was spontaneous and endothermic process. Furthermore, OMWCNT having the highest herbicide adsorption capacity could be regenerated and reused at least five times. This study showed that carbon nanotube-based adsorbents with magnetic and non-magnetic property were of high adsorption performance for the removal of DQ from water and could be promising adsorbent materials for the efficient removal of herbicides from wastewaters.

The efficient removal of mercury from aqueous media remains a severe challenge in ensuring environmental safety, especially for low-concentration mercury, which requires adsorbents with high mercury affinity. In this work, we reported a nanocomposite of β-cyclodextrin and three-dimensional graphene (3D CD@RGO) to enhance the adsorption affinity and capacity for mercury with low concentrations. Characterization of the nanocomposite revealed that cyclodextrin was well dispersed on the 3D graphene support structure to provide highly exposed hydroxyl groups. Adsorption experiments showed that CD@RGO exhibited different adsorption behaviors for mercury within different concentration ranges of 0.2–4.0 mg/L and 4.0–10.0 mg/L, and the adsorption affinity for the former range (KL = 10.05 L/mg) was 1.5 times higher than that for the latter range (KL = 6.69 L/mg). Moreover, CD@RGO had a high adsorption efficiency of 96.6% with a superb adsorption affinity (172.09 L/g) at Ce = 0.01 mg/L, which is 6.70 and 41.25 times higher than that of RGO and RCD (physical mixture of RGO and cyclodextrin), respectively, indicating a synergistic effect of CD@RGO for mercury adsorption. This enhancement can be attributed to the transformation of the adsorption mechanism from the outer-sphere force of electrostatic interaction in RGO to the inner-sphere surface complexation in CD@RGO.

There is a need to develop highly efficient materials for capturing uranium from nuclear wastewater. Here, 5-methylbenzotriazole modified graphene oxide (MBTA-GO) was used to adsorb U(VI) from aqueous solution. By the trials of different conditions, we found that the removal of U(VI) from acidic solution was strongly dependent on pH but independent of ionic strength. The U(VI) adsorption was perfectly conformed to the pseudo-second-order kinetics and the adsorption isotherms were simulated by the Langmuir model well. A high removal capacity (qₘₐₓ = 264 mg/g) for U(VI) at pH 3.5 was obtained. XPS, EXAFS analyses and DFT calculations revealed that the mechanism of uranium capture was ascribed to (i) the surface complexation by benzotriazole and carboxyl groups (providing lone pair electrons) on MBTA-GO and (ii) enhanced synergistic coordination ability of delocalized π-bond of triazole group toward U due to the transfer of electrons from graphene sheet to benzotriazole. DFT calculations further demonstrated that benzotriazole displayed stronger binding with U(VI) compared to carboxyl group due to higher binding energy of [Side/Surface-U-MBTA-GO] (79.745, 54.986 kcal/mol) than [MBTA-GO–COOH–U] (27.131 kcal/mol). This work will provide valuable insight into designing novel nitrogen-containing adsorbents for practical application in wastewater treatment.

In this study, graphene aerogel (GA) was successfully prepared through a simple hydrothermal method. The resulting GA exhibited a porous network structure with a large specific surface area (350.8 m²/g), ultra-light mass and easy separation from water. The pHIEP value of the GA was estimated to be 3.5. The adsorption process and the factors that affect adsorption capacity were studied. The adsorption could be conducted in a wide pH range from 2.0 to 7.0. The maximum adsorption capacity of GA towards U(VI) at pH 4.0 and T = 298 K was 238.67 mg/g calculated from the Langmuir model. The GA had greatly rapid adsorption property for the removal of U(VI) at pH 4.0. Kinetic data showed good correlation with pseudo-second-order equation. Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry characterizations showed that GA adsorbed U(VI) through chemical interaction by oxygen-containing and nitrogen-containing groups functional groups. The results show that GA has excellent application potential as an adsorbent material for removing U(VI) from aqueous solution.

Soil organic matter (SOM) is the principal aggregating agent for soil aggregation and also the main adsorbent for organochlorine pesticides (OCPs) such as dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH), which may thereby affect OCP distribution in soils subjected to different land use types. However, the potential effects of land use on SOM and OCP distribution patterns in soil aggregates are not well understood. In this study, soils from farmlands and barelands in the Danjiangkou Reservoir area were analyzed to determine the influence of land use on OCP distribution and composition in different aggregate fractions (>3, 1–3, 0.25–1, and <0.25 mm). The results showed that the levels of ∑DDTs ranged from 9.01 to 27.48 with a mean of 14.40 ng g⁻¹, and ∑HCHs ranged from 2.06 to 4.66 with a mean of 3.19 ng g⁻¹ in farmland soils. In comparison, bareland soils were less contaminated, with total DDTs and HCHs fell in the range of 0.75–5.01 ng g⁻¹ and not detected (n.d.)-1.40 ng g⁻¹ respectively. In regard to the distribution patterns in soil aggregates, the residual levels of ∑DDTs and ∑HCHs tended to a certain degree to enrich in microaggregates (<0.25 mm) relative to bulk soils. A further analysis revealed that the enrichment of ∑DDTs and ∑HCHs in microaggregates were mainly attributed to the accumulation of p,p'-DDE and β-HCH. Moreover, SOM was found also enriched in microaggregates. The enrichment of SOM was significantly and positively correlated with these of ∑DDTs, ∑HCHs, and the dominant metabolites (i.e., DDE and β-HCH) in both land use types. Such results indicated that the variations in behavior of OCPs could be linked to the processes of soil aggregate turnover. These findings may help to enrich the theory of soil OCPs sequestration and establish targeted strategies to mitigate their health risks in the environment.

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.