Significant concerns have been raised regarding to the pollution of antibiotics in recent years due to the abuse of antibiotics and their high detection rate in water. Herein, a novel super adsorbent, boronic acid-modified bacterial cellulose microspheres with a size of 415 μm in diameter was prepared through a facile water-in-oil emulsion method. The adsorbent was characterized by atomic force microscopy, scanning electron microscopy, and fourier transform infrared spectroscopy analyses to confirm its properties. The microspheres were applied as packing materials for the adsorption of tetracycline (TC) from an aqueous solution and hoggery sewer via the reversible covalent interaction between cis-diol groups in TC molecules and the boronic acid ligand. TC adsorption performance had been systemically investigated under various conditions, including the pH, temperature, TC concentration, contact time, and ionic strength. Results showed that the adsorption met pseudo-second-order, Elovich kinetic model and Sips, Redlich-Peterson isothermal models. And the adsorption process was spontaneous and endothermic, with the maximum TC adsorption capacity of 614.2 mg/g. After 18 adsorption-desorption cycles, the adsorption capacity remained as high as 84.5% compared with their original adsorption capacity. Compared with other reported adsorption materials, the microspheres had high adsorption capacity, a simple preparation process, and excellent recovery performance, demonstrating great potential in application on TC removal for water purification and providing new insights into the antibiotic's adsorption behavior of bacterial cellulose-based microspheres.

A biochar (BC) harbored Ag₃PO₄/α-Fe₂O₃ type-Ⅰ heterojunction (Ag-Fe-BC) was prepared by a hydrothermal-impregnation method to transfer active center of heterojunctions. The electrochemical and spectroscopic tests demonstrated that BC enhanced the catalytic performance of the heterojunction by enhancing photocurrent, reducing fluorescence intensity, and facilitating separation of electron-hole pairs. The photocatalytic activity showed the Ag-Fe-BC (5:1:3) could degrade Rhodamine B (20 mg/L) by up to 92.7%, which was 3.35 times higher than Ag₃PO₄/α-Fe₂O₃. Tetracycline and ciprofloxacin (20 mg/L) were degraded efficiently by 58.3% and 79.4% within 2 h, respectively. Electron paramagnetic resonance and scavenging experiments confirmed the major reactive oxygen species (ROS) consisted of singlet oxygen (¹O₂) and superoxide (·O₂⁻). Excellent RhB adsorption and electrons capturing capacity of BC facilitated electron-hole pairs separation and ROS transferring to target organics followed by elevated degradation. Thus, a facile method was proposed to synthesize a highly efficient visible-light responsive photocatalyst for degradation of various organics in water.

The concentration of persistent organic pollutants (POPs) makes remarkable difference to environmental fate. In the field of passive sampling, the partition coefficients between polystyrene-divinylbenzene resin (XAD) and air (i.e., KXAD₋A) are indispensable to obtain POPs concentration, and the KXAD₋A is generally thought to be governed by temperature and molecular structure of POPs. However, experimental determination of KXAD₋A is unrealistic for countless and novel chemicals. Herein, the Abraham solute descriptors of poly parameter linear free energy relationship (pp-LFER) and temperature were utilized to develop models, namely pp-LFER-T, for predicting KXAD₋A values. Two linear (MLR and LASSO) and four nonlinear (ANN, SVM, kNN and RF) machine learning algorithms were employed to develop models based on a data set of 307 sample points. For the aforementioned six models, R²ₐdⱼ and Q²ₑₓₜ were both beyond 0.90, indicating distinguished goodness-of-fit and robust generalization ability. By comparing the established models, the best model was observed as the RF model with R²ₐdⱼ = 0.991, Q²ₑₓₜ = 0.935, RMSEₜᵣₐ = 0.271 and RMSEₑₓₜ = 0.868. The mechanism interpretation revealed that the temperature, size of molecules and dipole-type interactions were the predominant factors affecting KXAD₋A values. Concurrently, the developed models with the broad applicability domain provide available tools to fill the experimental data gap for untested chemicals. In addition, the developed models were helpful to preliminarily evaluate the environmental ecological risk and understand the adsorption behavior of POPs between XAD membrane and air.

Garden pruning waste is becoming a problem that intensifies the garbage siege. It is of great significance to purify polluted water using biochar prepared from garden pruning waste. Herein, the interaction mechanism between BPS and oriental plane tree biochar (TBC) with different surface functional groups was investigated by adsorption experiments, spectroscopic analysis and theoretical calculations. Adsorption kinetics and isotherm of BPS on TBC can be satisfactorily fitted into pseudo-second-order kinetic and Langmuir models, respectively. A rapid adsorption kinetic toward BPS was achieved by TBC in 15 min. As compared with TBC prepared at low temperature (300 °C) (LTBC), the maximum adsorption capacity of TBC prepared at high temperature (600 °C) (HTBC) can be significantly improved from 46.7 mg g⁻¹ to 72.9 mg g⁻¹. Besides, the microstructure and surface functional groups of HTBC were characterized using SEM, BET-N₂, and XPS analysis. According to density functional theory (DFT) theoretical calculations, the higher adsorption energy of HTBC for BPS was mainly attributed to π-π interaction rather than hydrogen bonding, which was further supported by the analysis of FTIR and Raman spectra as well as the adsorption thermodynamic parameters. These findings suggested that by improving π-π interaction through high pyrolysis temperature, BPS could be removed and adsorbed by biochar with high efficacy, cost-efficiency, easy availability, and carbon-negative in nature, contributing to global carbon neutrality.

This study investigates the behavior of Tl in the Ría de Huelva (SW Spain), one of the most metal polluted estuaries in the world. Dissolved Tl concentration displayed a general decrease across the estuary during the dry season (DS); from 5.0 to 0.34 μg/L in the Tinto and Odiel estuaries, respectively, to 0.02 μg/L in the channel where the rivers join. A slighter decrease was observed during the wet season (WS) (from 0.72 to 0.14 μg/L to 0.02 μg/L) due to the dilution effect of rainfalls in the watersheds. These values are 3 orders of magnitude higher than those reported in other estuaries worldwide. Different increases in Tl concentrations with salinity were observed in the upper reaches of the Tinto and Odiel estuaries, attributed to desorption processes from particulate matter. Chemical and mineralogical evidences of particulate matter, point at Fe minerals (i.e., jarosite) as main drivers of Tl particulate transport in the estuary. Unlike other estuaries worldwide, where a fast sorption process onto particulate matter commonly takes place, Tl is mainly desorbed from particulate matter in the Tinto and Odiel estuaries. Thus, Tl may be released back from jarositic particulate matter across the salinity gradient due to the increasing proportion of unreactive TlCl⁰ and K⁺ ions, which compete for adsorption sites with Tl⁺ at increasing salinities. A mixing model based on conservative elements revealed a 6-fold increase in Tl concentrations related to desorption processes. However, mining spills like that occurred in May 2017 may contribute to enhance dissolved and particulate Tl concentrations in the estuary as well as to magnify these desorption processes (up to around 1100% of Tl release), highlighting the impact of the mine spill on the remobilization of Tl from the suspended matter to the water column.

The most prominent source of Cu contamination in soils is metal mining and processing, partly since the Middle Age. However, coal mining and combustion can also cause (some) Cu contamination. We studied the distribution of Cu concentrations and isotope ratios in soils of the Huaibei coal mining area. The contribution of the coal mining and combustion to total Cu concentrations in soil was determined with a two-end-member mixing model based on the distinct δ⁶⁵Cu values of the Cu emitted from coal mining and combustion and in native soil. The mean Cu concentration of 75 mg kg⁻¹ exceeded the local soil background value (round to 22.13 mg kg⁻¹). The similar δ⁶⁵Cu value of grass near the coal mining and combustion operation as in gangue and flying ash indicated a superficial Cu contamination. Mining input was the dominant source of Cu in the contaminated soils, contributing up to 95% and on average 72% of the total Cu in the topsoils. The mining-derived Cu was leached to a depth of 65 cm, where still 29% of the Cu could be attributed to the mining emissions. Grasses showed lower δ⁶⁵Cu values than the topsoils, because of the preferential uptake of light Cu isotopes. However, the Δ⁶⁵Cugᵣₐₛₛ₋ₛₒᵢₗ was lower in the contaminated than the uncontaminated area because of superficial adsorption of isotopically heavy Cu from the mining emissions. Overall, in this study the distinct δ⁶⁵Cu values of the mining-derived Cu emissions and the native soil allowed for the quantification of the mining-derived Cu and had already reached the subsoil and contaminated the grass by superficial adsorption in only 60 years of mining operation.

Goethite is a commonly found iron (hydr)oxide in soils and sediments that has been proven to possess abundant defects in structures. However, the underlying impact of these defects in goethite on arsenic immobilization remains unclear. In this study, goethite samples with abundant, moderate, and sparse defects were synthesized to evaluate their arsenic adsorption capacities. The characteristics of the defects in goethite were investigated by extended X-ray absorption fine structure (EXAFS), high angle annular dark field-scanning transmission electron microscopy-energy dispersion spectrum (HAADF-STEM-EDS) mapping, vibrating-sample magnetometry (VSM), and electron spin resonance (ESR). The characterization analysis revealed that the defects in as-synthesized goethite primarily existed in the form of Fe vacancies. Batch experiments demonstrated that the adsorption capacities of defect-rich goethite for As(V) and As(III) removal were 10.2 and 22.1 times larger than those of defect-poor goethite, respectively. The origin of the impact of Fe defects on arsenic immobilization was theoretically elucidated using density functional theory (DFT) calculations. The enhanced adsorption of goethite was attributed to the improvement of the arsenic affinity due to the Fe vacancy defect, thus considerably promoting arsenic immobilization. The findings of this study provide important insight into the migration and fate of arsenic in naturally occurring iron (hydr)oxides.

Slaughter wastewater is an important and wide range of environmental issues, and even threaten human health through meat production. A high efficiency and stability microsphere-immobilized Bacillus velezensis strain was designed to remove organic matter and inhibit the growth of harmful bacteria in process of slaughter wastewater. Bacillus velezensis was immobilized on the surface of sodium alginate (SA)/Polyvinyl alcohol (PVA)/Nano Zinc Oxide (Nano-ZnO) microsphere with the adhesion to bio-carrier through direct physical adsorption. Results indicated that SA/PVA/ZnO and SA/ZnO microspheres could inhibit E.coli growth with adding 0.15 g/L nano-ZnO and not affect Bacillus velezensis strain, and the removal the chemical oxygen demand (COD) rates of SA/PVA/ZnO microsphere immobilized cells are 16.99%, followed by SA/ZnO (13.69%) and free bacteria (7.61%) from 50% concentration slaughter wastewater within 24 h at 37 °C, pH 7.0, and 120 rpm, a significant difference was found between the microsphere and control group. Moreover, when the processing time reaches 36 h, COD degradation of SA/PVA/ZnO microsphere is obviously higher than other groups (SA/PVA/ZnO:SA/ZnO:control vs 18.535 : 15.446: 10.812). Similar results were obtained from 30% concentration slaughter wastewater. Moreover, protein degradation assay was detected, and there are no significant difference (SA/PVA/ZnO:SA/ZnO:control vs 35.4 : 34.4: 36.0). The design of this strategy could greatly enhance the degradation efficiency, inhibit the growth of other bacteria and no effect on the activity of protease in slaughter wastewater. These findings suggested that the nano-ZnO hydrogel immobilization Bacillus velezensis system wastewater treatment is a valuable alternative method for the remediation of pollutants from slaughter wastewater with a novel and eco-friendly with low-cost investment as an advantage.

Targeting the removal of Pb²⁺ in wastewater, cellulosic materials were carbonized in an aerobic environment and activated via ion exchange. The maximum adsorption capacity reached 243.5 mg/g on an MCC-derived adsorbent activated with sodium acetate. The modified porous properties improved the adsorption capacity. The capacity could be completely recovered five times through elution with EDTA. Because of the negative effects of Ni, Mg, and Ca elements, the adsorption capacities of activated carbonized natural materials were lower than that of pure cellulose. N₂ adsorption measurement showed that the adsorbent had a large specific surface area as well as abundant micropores and 4-nm-sized mesopores. FTIR and surface potential results proved that carboxyl group was generated in the aerobic carbonization, and was deprotonated during ion exchange. This adsorbent consisted of C–C bonds as the building blocks and hydrophilic groups on the surface. XPS results demonstrated that the Pb 4f binding energies were reduced by 0.7–0.8 eV due to the interaction between Pb²⁺ and the activated adsorbent, indicating that the carboxylate groups bonded with Pb²⁺ through coordination interactions. Pseudo-second-order and Elovich kinetic models were well fitted with the adsorption processes on the pristine and activated carbonized adsorbents, indicative of chemisorption on heterogeneous surfaces. The Freundlich expression agreed well with the data measured, and the pristine and activated adsorbents had weak and strong affinities for Pb²⁺, respectively. The Pb²⁺ adsorption process was exothermic and spontaneous, and heat release determined the spontaneity. The adsorption capacity is attributed to the carboxylate groups and pores generated in the aerobic oxidation and ion exchange procedures.

Modification of biochar by low-cost iron sources has gained increasing attention to improve pollutants removal performance and reduce production costs compared to conventional chemical modifications. While such iron sources generally have complex compositions, their effects on properties of the iron-biochar composite are not well investigated. This study produced an iron-biochar (RBC) composite from co-pyrolysis of incinerated sewage sludge ash (ISSA) and peanut shell, and examined the role of silica with widespread existence in ISSA and other low-cost iron sources on properties of the iron-biochar composite relevant to As(III)/As(V) removal. Silica was found to react with iron during the pyrolysis process at 850 °C and formed iron silicon at the expense of producing zero valent iron and Fe₃O₄ which resulted in a poorer removal efficacy for As(III) and As(V) compared to the iron-biochar (FBC) made from pure Fe₂O₃ and peanut shell. Moreover, a high leaching of reactive silica from RBC was observed which affected the formation of corrosion products of ZVI and competed with arsenic for active adsorption sites. Despite this, RBC still exhibited a maximum adsorption capacity of 17.44 and 57.56 mg/g towards As(III) and As(V) respectively at pH 3.0. Overall, this study provides an interesting insight into upcycling ISSA into useful media for sorptive removal of arsenic from aqueous solutions.