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.

Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO₄²⁻) and selenite (SeO₃²⁻) to red Se(-S)⁰, and arsenate (AsO₄³⁻) to arsenite (AsO₃³⁻). The release of H₂S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As₂S₃. When As and Se oxyanions were mixed, both As–S and Se(-S)⁰ biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (−24 to −38 mV). Kinetic analysis indicated the following reduction yields: SeO₃²⁻ (90%), AsO₄³⁻ (60%), and SeO₄²⁻ (<10%). The mix of SeO₃²⁻ with AsO₄³⁻ led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO₄²⁻ incubated with AsO₄³⁻ boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

In this study, magnetic biochar (MAB) and humic acid (HA)-coated magnetic biochar produced from apple branches without and after cellulase hydrolysis (HMAB and CHMAB, respectively) were prepared and tested as adsorbents of enrofloxacin (ENR) and moxifloxacin (MFX) in aqueous solution. Compared with MAB and HMAB, novel adsorbent CHMAB possessed a superior mesoporous structure, greater graphitization degree and abundant functional groups. When antibiotic solutions ranged from 2 to 20 mg L⁻¹, the theoretical maximum adsorption capacities of CHMAB for ENR and MFX were 48.3 and 61.5 mg g⁻¹ at 35 °C with adsorbent dosage of 0.4 g L⁻¹, respectively, while those of MAB and HMAB were 39.6 and 54.4 mg g⁻¹, and 44.7 and 59.0 mg g⁻¹, respectively. The pseudo-second-order kinetic model and Langmuir model presented a better fitting to the spontaneous and endothermic adsorption process. The maximum adsorption capacity of ENR and MFX onto CHMAB was achieved at initial pH values of 5 and 8, respectively. Additionally, the adsorption capacity of ENR and MFX decreased with increasing concentrations of K⁺ and Ca²⁺ (0.02–0.1 mol L⁻¹). Synergism between the pore-filling effect, π-π electron-donor-acceptor interactions, regular and negative charge-assisted H-bonding, surface complexation, electrostatic interactions and hydrophobic interactions may dominate the adsorption process. This study demonstrated that a novel magnetic biochar composite prepared through pyrolysis of agricultural waste lignocellulose hydrolyzed by cellulase in combination with HA coating was a promising adsorbent for eliminating quinolone antibiotics from aqueous media.

Per-and polyfluoroalkyl substances (PFASs) have attracted extensive attention since this century due to their wide distribution, persistence, bioaccumulation/biomagnification potential, and (eco)toxicity. In the present study, we investigated the sorption kinetics, sorption isotherms and desorption behaviors of legacy and emerging PFASs with different chain lengths and functional end groups onto marine sediments at four different salinities (0, 10, 20, and 30 practical salinity units (psu)). Results revealed that the sorption of PFASs onto sediment can be well described by the pseudo-second-order kinetic model. PFASs sorption was influenced by both compound-specific and solution-specific parameters. The distribution coefficient (Kd) for PFASs were increased with the increase of perfluorocarbon chain length and salinity, suggesting that hydrophobic and electrostatic interactions were involved in the adsorption process. 6:2 FTSA showed the lowest adsorption among PFASs with eight carbon atoms (6:2 FTSA, PFOA and PFOS). The increase of perfluorocarbon chain length of PFASs and salinity would result in the decrease of desorption rate of PFASs from sediment. In addition, PFCAs were desorbed more easily from the sediment than the PFSAs with the same perfluorocarbon chain length at all salinity groups. The present study demonstrated that salinity can apparently influence the fate of PFASs in aquatic environment and provided valuable data for modeling the fate of PFASs in real environment.

The current study is the first attempt to prepare nanocomposites of Eleocharis dulcis biochar (EDB) with nano zero-valent Copper (nZVCu/EDB) and magnetite nanoparticles (MNPs/EDB) for batch and column scale sequestration of Congo Red dye (CR) from synthetic and natural water. The adsorbents were characterized with advanced analytical techniques. The impact of EDB, MNPs/EDB and nZVCu/EDB dosage (1–4 g/L), pH (4–10), initial concentration of CR (20–500 mg/L), interaction time (180 min) and material type to remove CR from water was examined at ambient temperature. The CR removal followed sequence of nZVCu/EDB > MNPs/EDB > EDB (84.9–98% > 77–95% > 69.5–93%) at dosage 2 g/L when CR concentration was increased from 20 to 500 mg/L. The MNPs/EDB and nZVCu/EDB showed 10.9% and 20.1% higher CR removal than EDB. The adsorption capacity of nZVCu/EDB, MNPs/EDB and EDB was 212, 193 and 174 mg/g, respectively. Freundlich model proved more suitable for sorption experiments while pseudo 2nd order kinetic model well explained the adsorption kinetics. Fixed bed column scale results revealed excellent retention of CR (99%) even at 500 mg/L till 2 h when packed column was filled with 3.0 g nZVCu/EDB, MNPs/EDB and EDB. These results revealed that nanocomposites with biochar can be applied efficiently for the decontamination of CR contaminated water.

Plant uptake is an important process in determining the transfer of pesticides through a food chain. Understanding how crops take up and translocate pesticides is critical in developing powerful models to predict pesticide accumulation in agricultural produce and potential human exposure. Herein, wheat was selected as a model plant species to investigate the uptake and distribution of eleven widely used pesticides in a hydroponic system as a function of time for 144 h. The time-dependent uptake kinetics of these pesticides were fitted with a first-order 1-compartment kinetic model. During 144 h, flusilazole and difenoconazole, with relative high log Kₒw (3.87 and 4.36, respectively), displayed higher root uptake rate constants (k). To clarify the role of root lipid content (fₗᵢₚ) in plant accumulation of pesticides, we conducted a lipid normalization meta-analysis using data from this and previous studies, and found that the fₗᵢₚ value was an important factor in predicting the root concentration factor (RCF) of pesticides. An improved correlation was observed between log RCF and log fₗᵢₚKₒw (R² = 0.748, N = 26, P < 0.001), compared with the correlation between log RCF and log Kₒw (R² = 0.686, N = 26, P < 0.001). Furthermore, the hydrophilic pesticides (e.g. log Kₒw < 2) were found to reach partition equilibrium faster than lipophilic pesticides (e.g. log Kₒw > 3) during the uptake process. The quasi-equilibrium factor (αₚₜ) was inversely related to log Kₒw (R² = 0.773, N = 11, P < 0.001) suggesting a hydrophobicity-regulated uptake equilibrium. Findings from this study could facilitate crop-uptake model optimization.

Excessive copper (Cu) in contaminated soil and groundwater has attracted continuous attentions due to the bioaccumulation and durability. In this study, the feasibility of remediation of heavy metal pollution in soil and groundwater was investigated using hydroxyapatite/calcium silicate hydrate (HAP/C–S–H) recovered from phosphorus-rich wastewater in farmland. The results show that the pH has a strong effect on copper removal from Cu-contaminated groundwater but the impact of ion strength on the removal is weak. In general, high pH and low ion strength give better results in copper removal. Kinetic and isotherm data from the study fit well with Pseudo-second-order kinetic model and Langmuir isotherm model, respectively. The maximum adsorption capacity of HAP/C–S–H (138 mg/g) was higher than that of C–S–H (90.3 mg/g) when pH value, temperature, and ionic strength were 5, 308 K, and 0.01 M, respectively. Thermodynamics results indicate that Cu removal is a spontaneous and endothermic process. X-ray diffraction (XRD) results show that the mechanism of copper removal involves physical adsorption, chemical precipitation and ion exchange. For the remediation of Cu-contaminated soil, 76.3% of leachable copper was immobilized by HAP/C–S–H after 28 d. Acid soluble Cu, the main contributor to biotoxicity, decreased significantly while reducible and residual Cu increased. After immobilization, the acid neutralization capacity of the soil increased and the dissolution of copper was substantially reduced in near-neutral pH. It can be concluded that HAP/C–S–H is an effective, low-cost and eco-friendly reagent for in-situ remediation of heavy metal polluted soil and groundwater.

Magnetic biochars were prepared by chemical co-precipitation of Fe³⁺/Fe²⁺ onto rice straw (M-RSB) and sewage sludge (M-SSB), followed by pyrolysis treatment, which was also used to prepare the corresponding nonmagnetic biochars (RSB and SSB). The comparison of adsorption characteristics between magnetic and nonmagnetic biochars was investigated as a function of pH, contact time, and initial Cd²⁺ concentration. The adsorption of nonmagnetic biochars was better described by pseudo-second-order kinetic model, and the adsorption of RSB and SSB was better described by Langmuir and Freundlich models, respectively. Magnetization of the biochars did not change the applicability of their respective adsorption models, but reduced their adsorption capabilities. The maximum capacities were 42.48 and 4.64 mg/g for M-RSB and M-SSB, respectively, underperforming their nonmagnetic counterparts of 58.65 and 7.22 mg/g for RSB and SSB. Such a reduction was fundamentally caused by the decreases in the importance of cation-exchange and Cπ-coordination after magnetization, but the Fe-oxides contributed to the precipitation-dependent adsorption capacity for Cd²⁺ on magnetic biochars. The qualitative and quantitative characterization of adsorption mechanisms were further analyzed, in which the contribution proportions of cation-exchange after magnetization were reduced by 31.9% and 12.1% for M-RSB and M-SSB, respectively, whereas that of Cπ-coordination were reduced by 3.4% and 31.1% for M-RSB and M-SSB, respectively. These reductions suggest that for adsorbing Cd²⁺ the choice of conventional biochar was more relevant than whether the biochar was magnetized. However, magnetic biochars are easily separated from treated solutions, depending largely on initial pH. Their easy of separation suggests that magnetic biochars hold promise as more sustainable alternatives for the remediation of moderately Cd-contaminated environments, such as surface water and agriculture soil, and that magnetic biochars should be studied further.

Microplastics are known to be associated with co-contaminants, but little is understood about the mechanisms by which these chemicals are transferred from ingested plastic to organisms. This study simulates marine avian gastric conditions in vitro to examine the bioaccessibility of authigenic metals (Fe, Mn) and trace metals (Co, Pb) that have been acquired by polyethylene microplastic pellets from their environment. Specifically, different categories of pellet were collected from beaches in Cornwall, southwest England, and exposed to an acidified saline solution of pepsin (pH ∼ 2.5) at 40 °C over a period of 168 h with extracted metal and residual metal (available to dilute aqua regia) analysed by ICP-MS. For Fe, Mn and Co, kinetic profiles consisted of a relatively rapid initial period of mobilisation followed by a more gradual approach to quasi-equilibrium, with data defined by a diffusion model and median rate constants ranging from about 0.0002 (μg L⁻¹)⁻¹ h⁻¹ for Fe to about 7 (μg L⁻¹)⁻¹ h⁻¹ for Co. Mobilisation of Pb was more complex, with evidence of secondary maxima and re-adsorption of the metal to the progressively modified pellet surface. At the end of the time-courses, maximum total concentrations were 38.9, 0.81, 0.014 and 0.10 μg g⁻¹ for Fe, Mn, Co and Pb, respectively, with maximum respective percentage bioaccessibilities of around 60, 80, 50 and 80. When compared with toxicity reference values for seabirds, the significance of metals acquired by microplastics from the environment and exposed to avian digestive conditions is deemed to be low, but studies of a wider range of plastics and metal associations (e.g. as additives) are required for a more comprehensive risk assessment.

Persistent organic pollutants (POPs) have gained heightened attentions in recent years owing to their persistent property and hazard influence on wild life and human beings. Removal of POPs using varieties of multifunctional materials have shown a promising prospect compared with conventional treatments. Herein, three main categories, including thermal degradation, electrochemical remediation, as well as photocatalytic degradation with the use of diverse catalytic materials, especially the recently developed prominent ones were comprehensively reviewed. Kinetic analysis and underlying mechanism for various POPs degradation processes were addressed in detail. The review also systematically documented how catalytic performance was dramatically affected by the nature of the material itself, the structure of target pollutants, reaction conditions and treatment techniques. Moreover, the future challenges and prospects of POPs degradation by means of multiple multifunctional materials were outlined accordingly. Knowing this is of immense significance to enhance our understanding of POPs remediation procedures and promote the development of novel multifunctional materials.