Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^-1) on ¹³⁷Cs adsorption-desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26-99.97%) of added ¹³⁷Cs (3.7 × 10³-7.03 × 10⁵ Bq l^-1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K_ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K_ads and soil pH was observed. The ¹³⁷Cs adsorption-desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09-0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Contributions of adsorption,bioreduction and desorption to uranium immobilization by extracellular polymeric substances

● EPS immobilizes U(VI) via adsorption, bioreduction and desorption. ● This work provides a framework to quantify the three immobilization processes. ● The non-equilibrium adsorption of U follows pseudo-second-order kinetics. ● The equilibrium adsorption of U followed Langmuir and Freundlich isotherms. Hexavalent uranium (U(VI)) can be immobilized by various microbes. The role of extracellular polymeric substances (EPS) in U(VI) immobilization has not been quantified. This work provides a model framework to quantify the contributions of three processes involved in EPS-mediated U(VI) immobilization: adsorption, bioreduction and desorption. Loosely associated EPS was extracted from a pure bacterial strain, Klebsiella sp. J1, and then exposed to H₂ and O₂ (no bioreduction control) to immobilize U(VI) in batch experiments. U(VI) immobilization was faster when exposed to H₂ than O₂ and stabilized at 94% for H₂ and 85% for O₂, respectively. The non-equilibrium data from the H₂ experiments were best simulated by a kinetic model consisting of pseudo-second-order adsorption (k_a = 2.87 × 10⁻³ g EPS·(mg U)⁻¹·min⁻¹), first-order bioreduction (k_b = 0.112 min⁻¹) and first-order desorption (k_d = 7.00 × 10⁻³ min⁻¹) and fitted the experimental data with R² of 0.999. While adsorption was dominant in the first minute of the experiments with H₂, bioreduction was dominant from the second minute to the 50^th min. After 50 min, adsorption was negligible, and bioreduction was balanced by desorption. This work also provides the first set of equilibrium data for U(VI) adsorption by EPS alone. The equilibrium experiments with O₂ were well simulated by both the Langmuir isotherm and the Freundlich isotherm, suggesting multiple mechanisms involved in the interactions between U(VI) and EPS. The thermodynamic study indicated that the adsorption of U(VI) onto EPS was endothermic, spontaneous and favorable at higher temperatures.     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r²=0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK_FOC values of 6.02 to 6.42(μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C_e, the BC had higher K_oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C_e=0.05 S_w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

• DPAA sorption data was found to fit the Freundlich equation. • K_f was significantly positive correlated with oxalate-extractable Fe₂O₃. • Ligand exchange was the main mechanism for DPAA sorption on soils. • Bidentate binuclear and monodentate mononuclear DPAA bonds were identified. Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, K_f, was significantly and positively correlated with oxalate-extractable Fe₂O₃. The K_f values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the K_f values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in K_f to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (²C) and monodentate mononuclear (¹V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that ²C and ¹V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of ¹V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.     

Assessment of mobile and potential mobile trace elements extractability in calcareous soils using different extracting agents

• DTPA and NH₄OAc, HNO₃ and EDTA, and MgCl₂ and NH₄NO₃ had similar behavior. • In NH₄OAc, DTPA, and EDTA, the possibility of re-adsorption of trace elements is low. • CaCl₂ may be more suitable than other extracts in calcareous soils. Understanding trace elements mobility in soils, extracting agents, and their relationships with soil components, are essential for predicting their movement in soil profile and availability to plants. A laboratory study was conducted to evaluate extractability of cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), and zinc (Zn) from calcareous soils utilizing various extracting agents to be specific CaCl₂, DTPA, EDTA, HNO₃, MgCl₂, NaNO₃, NH₄NO₃, and NH₄OAc. Cluster analysis indicated that DTPA and NH₄OAc, HNO₃ and EDTA, and MgCl₂ and NH₄NO₃ extracting agents yielded comparative values, whereas NaNO₃ and CaCl₂ have shown different behavior than other extracting agents for all studied trace elements. The speciation of extracted trace elements in solutions indicated that in the CaCl₂, NaNO₃, NH₄NO₃, and MgCl₂ extracting agents most extracted Cd, Co, Ni, Zn, and part of Cu were as free ions and may be re-adsorbed on soils, leading to lower extractability, whereas, in the case of HNO₃ extracting agent, the likelihood of re-adsorption of trace elements may be little. The results of speciation of trace elements using NH₄OAc, DTPA, and EDTA extracting agents showed that Me-(Acetate)₃^–, Me-(Acetate)₂(aq), Me(DTPA)³⁻, Me(EDTA)²⁻, and MeH(EDTA)^– complexes dominated in solutions indicating that the extracted trace elements may not be re-adsorbed on soils, leading to higher extractability. The results of this study are useful for short and long-term evaluations of trace elements mobility and further environmental impacts.     

Heavy-metal adsorption by non-living biomass

The adsorption of some heavy metals onto the walls of harvested, washed, and dried non-living biomass cells of different Pseudomonas strains was studied at optimum experimental conditions using a simplified single component system. The Langmuir adsorption model was found to be a suitable approach to describe the system via multi-step processes. Isotherms measured at 30.0°C and pH 5.5 with [M]_total = 10-100 mM for tight, reversible Cr⁶⁺(aq), Ni²⁺(aq), Cu²⁺(aq) and Cd²⁺(aq) binding by the cell walls of the investigated biomass fit the Langmuir model and give the pH-independent stoichiometric site capacities ν_i and equilibrium constants K_i for metal binding at specific biomass sites i = A, B, C, and D. Tight binding sites A, B, and D of the non-living biomass are occupied by Cr^VI, sites A and C by Ni^II, sites A and D by Cd^II, and only site B by Cu^II. It is concluded that ν_i is a stoichiometric parameter that is independent of the magnitude of K_i for binding site i and that the studied heavy metals selectively and tightly bind at different biomass sites.     

Sorption of tetracycline to sediments and soils: assessing the roles of pH,the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL^- and L^2-). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

δ15N-stable isotope analysis of NHx: An overview on analytical measurements,source sampling and its source apportionment

• Challenges in sampling of NH₃ sources for d¹⁵N analysis are highlighted. • Uncertainties in the isotope-based source apportionment of NH₃ and NH₄⁺ are outlined. • Characterizing dynamic isotopic fractionation may reduce uncertainties of NH_x science. Agricultural sources and non-agricultural emissions contribute to gaseous ammonia (NH₃) that plays a vital role in severe haze formation. Qualitative and quantitative contributions of these sources to ambient PM_2.5 (particulate matter with an aerodynamic equivalent diameter below 2.5 µm) concentrations remains uncertain. Stable nitrogen isotopic composition (δ¹⁵N) of NH₃ and NH₄⁺ (δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺), respectively) can yield valuable information about its sources and associated processes. This review provides an overview of the recent progress in analytical techniques for δ¹⁵N(NH₃) and δ¹⁵N(NH₄⁺) measurement, sampling of atmospheric NH₃ and NH₄⁺ in the ambient air and their sources signature (e.g., agricultural vs. fossil fuel), and isotope-based source apportionment of NH₃ in urban atmosphere. This study highlights that collecting sample that are fully representative of emission sources remains a challenge in fingerprinting δ¹⁵N(NH₃) values of NH₃ emission sources. Furthermore, isotopic fractionation during NH₃ gas-to-particle conversion under varying ambient field conditions (e.g., relative humidity, particle pH, temperature) remains unclear, which indicates more field and laboratory studies to validate theoretically predicted isotopic fractionation are required. Thus, this study concludes that lack of refined δ¹⁵N(NH₃) fingerprints and full understanding of isotopic fractionation during aerosol formation in a laboratory and field conditions is a limitation for isotope-based source apportionment of NH₃. More experimental work (in chamber studies) and theoretical estimations in combinations of field verification are necessary in characterizing isotopic fractionation under various environmental and atmospheric neutralization conditions, which would help to better interpret isotopic data and our understanding on NH_x (NH₃ + NH₄⁺) dynamics in the atmosphere.     

土壤中铅的吸附-解吸行为研究进展

铅是重要的土壤重金属污染元素之一，了解铅在土壤中的物理化学行为，有利于预防和修复土壤的铅污染。土壤中铅的吸附-解吸行为，依吸附机理的不同，分为专性吸附和非专性吸附。土壤铅吸附的机理还存在不同的观点，如水解吸附／非水解吸附机理，单分子吸附／双分子吸附机理等。影响土壤中铅吸附-解吸行为的主要因素，有土壤矿物组成、土壤有机质、pH、温度、竞争离子等。文章最后对描述土壤铅吸附过程的主要数学方程(Langmuir方程、Freundlich方程和Temkin方程)作了论述。     

Cu/Cr co-stabilization mechanisms in a simulated Al2O3-Fe2O3-Cr2O3-CuO waste system

• Cu and Cr can be mostly incorporated into CuFe_xAl_yCr_2−x−yO₄ with a spinel structure. • Spinel phase is the most crucial structure for Cu and Cr co-stabilization. • Compared to Al, Fe and Cr are easier to be incorporated into the spinel structure. • ‘Waste-to-resource’ by thermal process at attainable temperatures can be achieved. Chromium slag usually contains various heavy metals, making its safe treatment difficult. Glass-ceramic sintering has been applied to resolve this issue and emerged as an effective method for metal immobilization by incorporating heavy metals into stable crystal structures. Currently, there is limited knowledge about the reaction pathways adopted by multiple heavy metals and the co-stabilization functions of the crystal structure. To study the Cu/Cr co-stabilization mechanisms during thermal treatment, a simulated system was prepared using a mixture with a molar ratio of Al₂O₃:Fe₂O₃:Cr₂O₃:CuO= 1:1:1:3. The samples were sintered at temperatures 600–1300°C followed by intensive analysis of phase constitutions and microstructure development. A spinel phase (CuFe_xAl_yCr_2−x−yO₄) started to generate at 700°C and the incorporation of Cu/Cr into the spinel largely complete at 900°C, although the spinel peak intensity continued increasing slightly at temperatures above 900°C. Fe₂O₃/Cr₂O₃ was more easily incorporated into the spinel at lower temperatures, while more Al₂O₃ was gradually incorporated into the spinel at higher temperatures. Additionally, sintered sample microstructures became more condensed and smoother with increased sintering temperature. Cu / Cr leachability substantially decreased after Cu/Cr incorporation into the spinel phase at elevated temperatures. At 600°C, the leached ratios for Cu and Cr were 6.28% and 0.65%, respectively. When sintering temperature was increased to 1300°C, the leached ratios for all metal components in the system were below 0.2%. This study proposes a sustainable method for managing Cu/Cr co-exist slag at reasonable temperatures.     

Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

Effects of organic acids on Cd adsorption and desorption by two anthropic soils

The objective of this experiment was to study the effects of malic, tartaric, oxalic, and citric acid on the adsorption and desorption characteristics of Cd by two typical anthropic soils (lou soil and irrigation-silted soil) in North-west China. Cadmium adsorption and desorption were studied under a range of temperatures (25°C, 30°C, 35°C, 40°C), organic acid concentrations (0.5–5.0 mmol·L^-1), and pH values (2–8). The results showed that the Cd adsorption capacity of the lou soil was significantly greater than that of the irrigation-silted soil. Generally, Cd adsorption increased as the temperature increased. In the presence of NaNO₃, the adsorption of Cd was endothermic with ΔH values of 31.365 kJ·mol^-1 for lou soil and 28.278?kJ·mol^-1 for irrigation-silted soil. The endothermic reaction indicated that H bonds were the main driving force for Cd adsorption in both soils. However, different concentrations of organic acids showed various influences on the two soils. In the presence of citric acid, chemical adsorption and van der Waals interactions were the main driving forces for Cd adsorption rather than H bonds. Although the types of organic acids and soil properties were different, the effects of the organic acids on the adsorption and desorption of Cd were similar in the two soils. The adsorption percentage of Cd generally decreased as organic acid concentrations increased. In contrast, the adsorption percentage increased as the pH of the initial solution increased. The exception was that adsorption percentage of Cd increased slightly as oxalic acid concentrations increased. In contrast, the desorption percentage of Cd increased with increasing concentrations of organic acids but decreased as the initial solution pH increased.     

Removal of fluoride from water using titanium-based adsorbents

Three adsorbents including TiO₂, Ti-Ce, and Ti-La hybrid oxides were prepared to remove fluoride from aqueous solution. The Ti-Ce and Ti-La hybrid adsorbents obtained by the hydrolysis-precipitation method had much higher sorption capacity for fluoride than the TiO₂ adsorbent prepared through hydrolysis. Rare earth (Ce and La) oxides and TiO₂ exhibited a synergistic effect in the hybrid adsorbents for fluoride sorption. The sorption equilibrium of fluoride on the three adsorbents was achieved within 4 h, and the pseudo-second-order model described the sorption kinetics well. The sorption isotherms fitted the Langmuir model well, and the adsorption capacities of fluoride on the Ti-Ce and Ti-La adsorbents were about 9.6 and 15.1 mg·g^-1, respectively, at the equilibrium fluoride concentration of 1.0 mg·L^-1, much higher than the 1.7 mg·g^-1 on the TiO₂. The sorption capacities of fluoride on the three adsorbents decreased significantly when the solution pH increased from 3 to 9.5. The electrostatic interaction played an important role in fluoride removal by the three adsorbents, and Fourier transform infrared (FTIR) analysis indicated that the hydroxyl groups on the adsorbent surface were involved in fluoride adsorption.     

Predicting non-carcinogenic hazard quotients of heavy metals in pepper (Capsicum annum L.) utilizing electromagnetic waves

• There was significant absorption of heavy metals by the pepper in contaminated soils. • The target hazard quotient (THQ) indices followed the order of Pb>Zn>>Cd » Ni. • Relationships exist between contaminated plants and electromagnetic wave. • PCA and random search can select the main spectra and predict THQ for each element. Given the tendency of heavy metals to accumulate in soil and plants, the purpose of this study was to determine the contamination levels of Cd, Ni, Pb, and Zn on peppers (leaves and fruit) grown in contaminated soils in industrial centers. For this purpose, we measured the uptake of the four heavy metals by peppers grown in the heavy metal contaminated soils throughout the four growth stages: two-leaf, growth, flowering, and fruiting, and calculated various vegetation indices to evaluate the heavy metal contamination potentials. Electromagnetic waves were also applied for analyzing the responses of the target plants to various heavy metals. Based on the relevant spectral bands identified by principal component analysis (PCA) and random search methods, a regression method was then employed to determine the most optimal spectral bands for estimating the target hazard quotient (THQ). The THQ was found to be the highest in the plants contaminated by Pb (THQ= 62) and Zn (THQ= 5.07). The results of PCA and random search indicated that the spectra at the bands of b₅₇₀, b₆₅₀, and b₇₆₀ for Pb, b₄₀₀ and b₁₀₃₀ for Ni, b₄₀₀ and b₈₈₀ for Cd, and b₅₆₀, b₉₁₀, and b₁₀₅₀ for Zn were the most optimal spectra for assessing THQ. Therefore, in future studies, instead of examining the amount of heavy metals in plants by chemical analysis in the laboratory, the responses of the plants to the electromagnetic waves in the identified bands can be readily investigated in the field based on the established correlations.     

Electro-catalytic activity of CeOx modified graphite felt for carbamazepine degradation via E-peroxone process

•CeO_x/GF-EP process had the better degradation efficiency than GF-EP process. •CeO_x/GF-EP process had the flexible application in the pH range from 5.0 to 9.0. •CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance. •The interfacial electron transfer process was revealed. E-peroxone (EP) was one of the most attractive AOPs for removing refractory organic compounds from water, but the high energy consumption for in situ generating H₂O₂ and its low reaction efficiency for activating O₃ under acidic conditions made the obstacles for its practical application. In this study, cerium oxide was loaded on the surface of graphite felt (GF) by the hydrothermal method to construct the efficient electrode (CeO_x/GF) for mineralizing carbamazepine (CBZ) via EP process. CeO_x/GF was an efficient cathode, which led to 69.4% TOC removal in CeO_x/GF-EP process with current intensity of 10 mA in 60 min. Moreover, CeO_x/GF had the flexible application in the pH range from 5.0 to 9.0, TOC removal had no obvious decline with decrease of pH. Comparative characterizations showed that CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance of GF. About 5.4 mg/L H₂O₂ generated in CeO_x/GF-EP process, which was 2.1 times as that in GF-EP process. The greater ozone utility was also found in CeO_x/GF-EP process. More O₃ was activated into hydroxyl radicals, which accounted for the mineralization of CBZ. An interfacial electron transfer process was revealed, which involved the function of oxygen vacancies and Ce³⁺/Ce⁴⁺ redox cycle. CeO_x/GF had the good recycling property in fifth times’ use.