The optimization of nickel ion (Ni2+) removal in aqueous solutions with various factors (initial Ni concentration, solution pH, adsorbent dosage, contact time), as affected by raw cow bone (RBO) and its biochar (bone char: BC; produced by pyrolysis processes at 500 °C and a residence time of 4 hours) as adsorbents was investigated by a three-level Box–Behnken model (BBM) under response surface methodology (RSM). A total of 29 experimental runs were set for each adsorbent, and the experimental data were fitted to the empirical model. To understand the Ni2+ adsorption processes better, the properties of RBO and BC were characterized using Fe-SEM, FT-IR, BET, XRD, and CHNS elemental analysis techniques. The BC characteristics showed that pyrolysis increased the specific surface area (by 100 times) and phosphate functional groups, but decreased the carbonate functional groups, and yielded a more irregular and rougher morphological surface compared to RBO. Based on BC's superior ion exchange mechanisms and physical electrostatic adsorption compared to RBO, the removal efficiency of Ni2+ by BC was higher in aqueous solutions. The numerical optimization of BBM revealed that the optimum removal by BC (82.56%) was obtained at an initial Ni2+ concentration of 30.79 mg L−1, pH of 6.99, adsorbent dose of 4.87 g L−1, and contact time of 57.82 min, with the desirability of "1". BC can be effectively used for Ni removal from Ni-contaminated aqueous solutions; still, the application of modification methods (e.g., physical and chemical activation) may be necessary to help remove more Ni2+ by BC.

Trivalent chromium [Cr(III)] and tannins serve as necessary substances in leather processing and coexist in tannery site, which lead to the chromium contamination in site soil when disposed improperly. However, coexisting tannins are very likely to complex with Cr(III) and affect its properties, ultimately changing the mobility of chromium in soil. In this study, tannic acid (TA) was selected to investigate the complexation with Cr(III) and the influence on the solubility and sorption of Cr(III) in soils. Then, the transport behavior and mechanism of Cr(III)-TA complexes in soil was clarified. Dialysis results showed that the increase of TA concentration and solution pH promoted the formation of complexed Cr(III). The results of UV–Vis absorption spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations indicated that the adjacent ionized phenolic hydroxyls in TA functioned as the binding sites with Cr(III) to form the Cr–O bonds and the degree of complexation increased with pH. The Cr(III)-TA complexes had higher solubility than free Cr(III) at pH ≥ 6.0. Batch sorption experiments demonstrated that the sorption capacity of Cr(III)-TA to soils with different pH was always lower than that of free Cr(III). These reasons led to the stronger mobility of Cr(III)-TA in soil columns than Cr(III). Our research reveals that the enhanced mobility of Cr(III) in soils coexisting with TA.

Distribution in ice is regarded as one of important transport modes for pollutants in seasonal freeze-up waters in cold regions. However, the distribution characteristics and mechanisms of fluorinated antibiotics as emerging contaminants during the water freezing process remain unclear. Here, florfenicol and norfloxacin were selected as model fluorinated antibiotics to investigate their ice-water distribution. Effects of antibiotic molecular structure on the distribution were explored through comparative studies with their non-fluorinated structural analogs. Results showed that phase changes during the ice growth process redistributed the antibiotics, with antibiotic concentrations in water 3.0–6.4 times higher than those in ice. The solute-rich boundary layer with a concentration gradient was presented at the ice-water interface and controlled by constitutional supercooling during the freezing process. The ice-water distribution coefficient (KIW) values of antibiotics increased by 34.8%–38.0% with a doubling of the cooling area. The solute distribution coefficient (Kbₛ) values of antibiotics at −20 °C were 65.6%–70.3% higher than at −10 °C. The KIW and Kbₛ values of all antibiotics were negatively correlated with their water solubilities. The fluorine substituents influenced the binding energies between antibiotics and ice, resulting in a 1.1-fold increase in the binding energy of norfloxacin on the ice surface relative to its structural analog pipemidic acid. The results provide a new insight into the transport behaviors of fluorinated pharmaceuticals in ice-water systems.

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.

Application of nanopesticides may substantially increase surface attachment and internalization of engineered nanoparticles (ENPs) in food crops. This study investigated the role of stomata in the internalization of silver nanoparticles (Ag NPs) using abscisic acid (ABA)-responsive ecotypes (Ler and Col-7) and ABA-insensitive mutants (ost1-2 and scord7) of Arabidopsis thaliana in batch sorption experiments, in combination with microscopic visualization. Compared with those of the ABA-free control, stomatal apertures were significantly smaller for the Ler and Col-7 ecotypes (p ˂ 0.05) but remained unchanged for the ost1-2 and scord7 mutants, after exposure to 10 μM ABA for 1 h. Generally Ag NP sorption to the leaves of the Ler and Col-7 ecotypes treated with 10 μM ABA was lower than that in the ABA-free control, mainly due to ABA-induced stomatal closure. The difference in Ag NP sorption with and without ABA was less pronounced for Col-7 than for Ler, suggesting different sorption behaviors between these two ecotypes. In contrast, there was no significant difference in foliar sorption of Ag NPs by the ost1-2 and scord7 mutants with and without ABA treatment. Ag NPs were widely attached to the Arabidopsis leaf surface, and found at cell membrane, cytoplasm, and plasmodesmata, as revealed by scanning electron microscopy and transmission electron microscopy, respectively. These results highlight the important role of stomata in the internationalization of ENPs in plants and may have broad implications in foliar application of nanopesticides and minimizing contamination of food crops by ENPs.

Cadmium (Cd) is one dangerous and widespread heavy metal that of great environmental concern. To cost-efficiently adsorb aqueous Cd under influence of various factors, this study succeeded in fabricating goethite-modified biochar (GBC) derived from distillers’ grains (DGs) for Cd sorption of different concentrations (10–100 mg L⁻¹) at pH of 3, 6 and 8 with and without microcystin-LR (MC-LR). Sorption kinetics and isotherms data revealed that Cd sorption capacity of GBC and unmodified BC increased as pH elevated from 3 to 6 but stabilized when pH further elevated to 8. Pseudo-second-order and Langmuir models more accurately fitted to sorption data for both BCs, implying monolayer chemisorption of Cd onto BCs. GBC exhibited more robust sorption for each Cd concentration than unmodified BC, with the maximum sorption capacity of around 28 mg g⁻¹ at neutral and weak alkaline pH. Notably, goethite-modification obviously increased bulk polarity, specific surface area, porosity and surface oxygenic group abundance of BC, thus strongly enhancing Cd sorption by creating more sorption sites mainly via pore-filling, electrostatic attraction, and also via complexation and cation exchange. Co-existing MC-LR of 100 μg L⁻¹ did not obviously affect Cd sorption by both BCs for most Cd levels at each pH, mostly because sorption mechanisms diverged between MC-LR and Cd to largely avoid their competition for sorption sties. Thus, goethite could modify DG-BC as promising and cost-efficient sorbent for Cd even with co-existing MC-LR, especially at neutral and weak alkaline pH that common in the nature. This study was greatly implicated in modifying and applying DG-BC for Cd immobilization in MC-LR laden waters with various pH circumstances.

Granular activated carbon (GAC) has been used to remove per- and polyfluoroalkyl substances (PFASs) from industrial or AFFF-impacted waters, but its effectiveness can be low because adsorption of short-chained PFASs is ineffective and its sites are exhausted rapidly by co-contaminants. To increase adsorption of anionic PFASs on GAC by electrostatic attractions, we modified GAC's surface with the cationic polymer poly diallyldimethylammonium chloride (polyDADMAC) and tested its capacity in complex water matrices containing dissolved salts and humic acid. Amending with concentrations of polyDADMAC as low as 0.00025% enhanced GAC's adsorption capacity for PFASs, even in the presence of competing ions. This suggests that electrostatic interactions with polyDADMAC's quaternary ammonium functional groups helped bind organic and inorganic ions as well as the headgroup of short-chain PFASs, allowing more overall PFAS removal by GAC. Evaluating the effect of polymer dose is important because excessive addition can block pores and reduce overall PFAS removal rather than increase it. To decrease the waste associated with this adsorption strategy by making the adsorbent viable for more than one saturation cycle, a regeneration method is proposed which uses low-power ultrasound to enhance the desorption of PFASs from the polyDADMAC-GAC with minimum disruption to the adsorbent's structure. Re-modification with the polymer after sonication resulted in a negligible decrease in the sorbent's capacity over four saturation rounds. These results support consideration of polyDADMAC-modified GAC as an effective regenerable adsorbent for ex-situ concentration step of both short and long-chain PFASs from real waters with high concentrations of competing ions and low PFAS loads.

Halogenated PAHs (HPAHs) are ubiquitous in the environment and have a toxicity similar to that of dioxin. Microplastics exist widely in the environment, and their sorption allows them to act as carriers of HPAHs, potentially changing the bioavailability of HPAHs. However, to the best of our knowledge related studies are limited. In this study, degrading bacteria of five HPAHs were cultivated from mangrove sediments. Among them, the Hyphomicrobium genus has good degradation ability on 9−BrAnt, 2−BrPhe and 2−ClPhe. The degradation process is in line with the first−order degradation kinetic characteristics. The kinetic equations of five kinds of HPAHs showed that the degradation half−lives are 0.65 days (2−BrFle), 0.79 days (9−ClPhe), 1.50 days (2−ClAnt), 5.94 days (9−BrPhe) and 14.1 days (9−BrAnt). The greater the number of benzene rings and the heavier the halogen substituents, the slower the degradation of HPAHs. The sorption of microplastics inhibited the biodegradation of HPAHs, and the degradation half−life of HPAHs will be extended from 0.65 to 14.1 days (the average is 4.59 days) to 1.71–9.93 days (average 5.40 days) for PA, 0.70–35.2 days (average 12.8 days) for PE, 6.02–28.2 (average 15.7 days) days for POM, and 4.60–24.0 (average 19.2 days) days for PP, which is mainly related to the partition coefficient between microplastics and water. This study provides a reference for reducing the uncertainty of the ecological risk assessment of HOCs in the aquatic environment.

Glyphosate (N-phosphonomethylglycine; GLP) and its main metabolite AMPA (aminomethylphosphonic acid), are frequently detected in relatively high concentrations in European agricultural topsoils. Glyphosate has a high sorption affinity, yet it can be detected occasionally in groundwater. We hypothesized that shrinkage cracks occurring after dry periods could facilitate GLP transport to greater depths where subsoil conditions slow further microbial degradation. To test this hypothesis, we simulated a heavy rainfall event (HRE) on a clay-rich arable soil. We applied 2.1 kg ha⁻¹ of 100% ¹³C₃, ¹⁵N-labeled GLP one day before the simulated rainfall event. Microbial degradation of translocated GLP over a 21-day period was assessed by quantifying ¹³C incorporation into phospholipid fatty acids. Microbial degradation potential and activity were determined by quantifying the abundance and expression of functional genes involved in the two known degradation pathways of GLP; to AMPA (goxA) or sarcosine (sarc). We confirmed that goxA transcripts were elevated in the range of 4.23 x 10⁵ copy numbers g⁻¹ soil only one day after application. The increase in AMPA associated with a rise in goxA transcripts and goxA-harboring microorganisms indicated that the degradation pathway to AMPA dominated. Based on ¹³C-enrichment 3 h after the HRE, fungi appeared to initiate glyphosate degradation. At later time points, Gram⁺-bacteria proved to be the main degraders due to their higher ¹³C-incorporation. Once GLP reached the subsoil, degradation continued but more slowly. By comparing GLP distribution and its microbial degradation in macropores and in the bulk soil, we demonstrated different time- and depth-dependent GLP degradation dynamics in macropores. This indicates the need for field studies in which soil properties relevant to GLP degradation are related to limiting environmental conditions, providing a realistic assessment of GLP fate in soils.

Tire-derived particles and polyethylene (PE) debris co-exist in estuaries and potentially deteriorate water quality. Chemicals can be emitted from tire-derived particles and resorb to PE debris. However, there was lack of information about the interaction (e.g., sorption and desorption) between tire-derived chemicals and PE debris. By combining batch sorption and desorption experiments along with in situ field deployment of PE sheets, we examined the utility of benzothiazoles (BTZs) sorbed in PE as suitable markers of tire-derived inputs. The sorptive characteristics and PE-water partition coefficients (often designated as Kₚₑw) of selected tire-derived marker candidates, i.e., polycyclic aromatic hydrocarbons (PAHs), benzothiophenes (BTPs) and BTZs, were measured. Moderately polar BTPs and BTZs (except for 2-(4-morpholinyl) benzothiazole) reached equilibrium within 2–8 days, compared to 20 days for nonpolar PAHs. The measure Kₚₑw values and octanol-water partition coefficients of PAHs and BTZs were linearly correlated with each other (r² > 0.80; p < 0.05). The desorption potentiality of PAHs and BTZs from tire particles is consistent with the hydrophilic properties of the target chemicals, while desorption ratios of BTZs and PAHs are 25–87% and <20%, respectively. Samplers with PE sheets as the sorbent phase were deployed in Hailing Bay, an urbanized estuary in South China, to measure concentrations of PAHs, BTPs and BTZs. Benzothiazoles sorbed in PE samples were associated with the massive utilization of automobile tires, while PAHs were linked to the boat maintenance facilities and BTPs were not detected in any tire particle and field PE samples. Therefore sorbed BTZs in PE can potentially serve as chemical markers of tire-derived inputs to estuaries.