Discharge of synthetic dyes from industries without treatment leads to major environmental problems. Present research highlighted the Mn-doped ZnO along with UV-induced photo degradation of Congo red (CR) dye through batch study. The synthesized Mn-doped ZnO (MDZO) was characterized by Transmission electron microscope (TEM) and Fourier transform infrared spectroscopy (FTIR). The results revealed that MDZO along with UV exposure degraded the CR dye up to 99.3% at concentration 4 mg/L, pH (7), adsorbent dose (0.6 g/L) and contact time (30 min). The degradation data nicely fitted with pseudo-secondary kinetics and the thermodynamic study suggest the said reaction is exothermic in nature. A statistical method, central composite design (CCD) was used to screen out the optimized condition of dye degradation. The interactions of main factors and optimal conditions were also evaluated by 3D surface plots. The statistical output clearly demonstrates that the dye degradation data is nicely fitted with very high goodness of fit and F value (86.19). Present research clearly suggested that Mn-doped ZnO along with UV could be an effective treatment towards degradation of Congo red dye.

The adsorption of radioactive iodine, which is capable of presenting high mobility in aquatic ecosystems and generating undesirable health effects in humans (e.g., thyroid gland dysfunction), was comprehensively examined using pristine spent coffee ground biochar (SCGB) and bismuth-impregnated spent coffee ground biochar (Bi@SCGB) to provide valuable insights into the variations in the adsorption capacity and mechanisms after pretreatment with Bi(NO₃)₃. The greater adsorption of radioactive iodine toward Bi@SCGB (adsorption capacity (Qₑ) = 253.71 μg/g) compared to that for SCGB (Qₑ = 23.32 μg/g) and its reduced adsorption capability at higher pH values provide evidence that the adsorption of radioactive iodine with SCGB and Bi@SCGB is strongly influenced by the presence of bismuth materials and the electrostatic repulsion between their negatively charged surfaces and negatively charged radioactive iodine (IO₃⁻). The calculated R² values for the adsorption kinetics and isotherms support that chemisorption plays a crucial role in the adsorption of radioactive iodine by SCGB and Bi@SCGB in aqueous phases. The adsorption of radioactive iodine onto SCGB was linearly correlated with the contact time (h¹/²), and the diffusion of intra-particle predominantly determined the adsorption rate of radioactive iodine onto Bi@SCGB (Cₛₜₐgₑ II (129.20) > Cₛₜₐgₑ I (42.33)). Thermodynamic studies revealed that the adsorption of radioactive iodine toward SCGB (ΔG° = −8.47 to −7.83 kJ/mol; ΔH° = −13.93 kJ/mol) occurred exothermically and that for Bi@SCGB (ΔG° = −15.90 to −13.89 kJ/mol; ΔH° = 5.88 kJ/mol) proceeded endothermically and spontaneously. The X-ray photoelectron spectroscopy (XPS) analysis of SCGB and Bi@SCGB before and after the adsorption of radioactive iodine suggest the conclusion that the change in the primary adsorption mechanism from electrostatic attraction to surface precipitation upon the impregnation of bismuth materials on the surfaces of spent coffee ground biochars is beneficial for the adsorption of radioactive iodine in aqueous phases.

Low-molecular-weight organic acids may significantly influence the mobility of metal in environment, but the kinetics are not fully understood and have not been quantified. In this study, the thermodynamic and kinetic effects of citric acid (CA) on the adsorption of Cd(II) and Ni(II) on goethite were investigated using batch-adsorption and stirred-flow experiments. A charge distribution and multisite complexation model (CD-MUSIC) and a thermodynamically based multi-rate kinetic model were employed to describe the adsorption behaviors. Two ternary surface complexes, (≡FeO)₂CitMe and (≡FeOH)₂MeCit²⁻, were involved in the adsorption. In addition, CA differed in its effects on Cd(II) and Ni(II) adsorption, enhancing Cd(II) adsorption but inhibiting Ni(II) adsorption at high levels. Kinetically, in the presence of CA, the adsorption of Cd(II) was faster than that of Ni(II). Increasing CA concentration led to faster Cd(II) adsorption, but resulted in the dissolution of the adsorbed Ni(II), possibly due to the much higher complexation constants of Ni-CA than of Cd-CA in aqueous phase. This finding implied that, in the rhizosphere, high level of CA may lead to more dissolution of Ni(II) than Cd(II); while in acidic ferrosol, CA may alleviate Cd(II) mobility and toxicity. The proposed mechanistic model sheds light on ion partition in the soil environment and may improve predictions thereof.

This study investigated the competitive adsorption mechanisms of pharmaceuticals (i.e., naproxen, diclofenac, and ibuprofen) toward the pristine and NaOH-activated biochars from spent coffee wastes (SCW) in lake water and wastewater effluent. The kinetic and isotherm studies revealed that the improved physicochemical characteristics and physically homogenized surfaces of the pristine SCW biochar through the chemical activation with NaOH were beneficial to the adsorption of pharmaceuticals (competitive equilibrium adsorption capacity (Qₑ, ₑₓₚ): NaOH-activated SCW biochar (61.25–192.07 μmol/g) > pristine SCW biochar (14.81–20.65 μmol/g)). The adsorptive removal of naproxen (Qₑ, ₑₓₚ = 14.81–18.81 μmol/g), diclofenac (Qₑ, ₑₓₚ = 15.73–20.00 μmol/g), and ibuprofen (Qₑ, ₑₓₚ = 16.20–20.65 μmol/g) for the pristine SCW biochar showed linear correlations with their hydrophobicity (log D at pH 7.0: ibuprofen (1.71) > diclofenac (1.37) > naproxen (0.25)). However, their Qₑ, ₑₓₚ values for the NaOH-activated SCW biochar (naproxen (176.39–192.07 μmol/g) > diclofenac (78.44–98.74 μmol/g) > ibuprofen (61.25–80.02 μmol/g)) were inversely correlated to the order of their log D values. These results suggest that the reinforced aromatic structure of the NaOH-activated SCW biochar facilitated the π-π interaction. The calculated thermodynamic parameters demonstrated that the competitive adsorption of pharmaceuticals on the NaOH-activated SCW biochar compared to pristine SCW biochar occurred more spontaneously over the entire pH (5.0–11.0) and ionic strength (NaCl: 0–0.125 M) ranges. These observations imply that the NaOH-activated SCW biochar might be potentially applicable for the removal of pharmaceuticals in lake water and wastewater effluent.

In China, more than 10,000 tons of bean-worm, which is rich in protein (68.5%) and essential amino acids (52.8%), is consumed annually. Thus, a large amount of bean-worm skin waste is generated, and is often indiscriminately disposed of, potentially causing environment problems. In this study, bean-worm skin (BWS) waste was pyrolyzed at 500 °C to produce biochar (BWS-BC), and the surface properties of BWS and BWS-BC were characterized using various spectroscopic techniques. Pb(II) adsorption properties of BWS and the corresponding biochar as a function of solution pH, contact time, and equilibrium concentration of Pb(II) were examined using adsorption isotherm, kinetics and thermodynamics studies. The maximum Pb(II) adsorption capacities based on the Langmuir isotherm model were calculated as 45 and 62 mg g⁻¹ for BWS and BWS-BC, respectively, which were comparable to the values obtained for biochars derived from other agro-wastes. The adsorption feasibility, favorability and spontaneity of Pb(II), as derived from the thermodynamic parameters, indicated that chemisorption and precipitation (e.g., hydroxypyromorphite) were the main adsorption mechanism in case of BWS and BWS-BC, respectively. Thus, conversion of BWS to biochar for Pb(II) adsorption can be considered as a feasible, promising and high value-added approach for BWS recycling.

The co-precipitation method was used to synthesize nano-magnetic adsorbent MnFe₂O₄ (nMFO), characterized through XRD, SEM, EDS, and BET techniques. The synthesized nMFO was used for hexavalent and trivalent chromium ions elimination from the aqueous phase. The optimum pH for the adsorption of Cr (VI) and Cr (III) was determined as 2 and 5, respectively. The chromium ions adsorption behavior was well interpreted through the pseudo-second order kinetics model. Furthermore, isotherm studies were conducted, and the obtained results indicated that Langmuir isotherm model could well justify the chromium ions adsorption process. Quick removal (less than 10 min) of both chromium ions and high removal efficiency were occurred using nMFO. The utmost adsorption capacity of trivalent and hexavalent chromium ions were determined as 39.6 and 34.84 mg g⁻¹, respectively. Thermodynamic studies on chromium adsorption revealed positive value for ΔH and negative value for ΔG, representing that chromium ions adsorption was an endothermic and spontaneous process. The multilinearity in the graphs of chromium ions adsorption was observed using intra-particle diffusion model. In this regard, the external mass transfer of chromium ions on synthesized nanoparticles was the important and controlling step in the adsorption process.

Metal pollution in estuaries represents a serious environmental challenge, especially in areas affected by industrial and mining activities. This study investigates the metal partitioning and availability of rare earth elements (REE), Y and other trace metals (Ag, Tl, U and Cs) in the Ria of Huelva estuary (SW Spain), strongly affected by mining and industrial activities. A 30 h monitoring campaign was performed collecting periodic water samples and deploying diffusive gradient in thin films (DGTs) devices to determine the main factors controlling metal availability. The dissolved concentrations of U (3118–3952 ng/L) and Cs (284–392 ng/L) were in the same order of magnitude than those reported in other estuaries and coastal waters worldwide, however, REE (26–380 ng/L), Y (15–109 ng/L), Ag (14–307 ng/L) and Tl (29–631 ng/L) concentrations exceeded these values for the same salinities. Unlike most metals (i.e. Ag, Tl, U, Cs), which were mainly found in the dissolved form (87–100% of total), REE and Y were found in the particulate phase (22–36% of total). Metal lability was mainly related to the concentration in the water column following this order: U>REE>Y>Ag>Tl. A similar binding mechanism was observed for Tl and Cd, due to its chemical affinity. This relationship between chemical properties and absorption by DGT-resin was also observed for REE (and Y), Rb and Sr, which may cause bioaccumulation upon persistent exposure, considering the ability of these metals to cross the biological membranes. The lability of metals predicted by geochemical codes did not coincide with absorption of labile metals by DGTs due probably to the instability of complexes in contact with the DGT membranes, the inability of metals to form thermodynamically stable complexes or the absorption of colloids. From this work it can be concluded that DGT passive sampling should complement traditional sampling to monitor metal availability in aquatic environments.

Porous carbon, which can be functionalized, is considered as a potential carbon material. Herein, two-dimensional (2D) nitrogen-doped magnetic Fe₃C/C (NMC) was prepared by a simple carbonization method using potassium humate (HA-K) as raw material. Remarkably, two templates, g-C₃N₄ and KCl, were formed in situ during the carbonization process, which provide the necessary conditions for the formation of 2D NMC. The NMC was comprehensively studied by different characterization methods. The results show that NMC has a large surface area and mesoporous structure. The prepared NMC-0.50 was used to test the removal performance of Cr(VI). The effects of pH value, coexisting ions and time on Cr(VI) removal performance were investigated, and the adsorption kinetics, isotherm and thermodynamics were studied. The results showed that the adsorption isotherm model of NMC-50 accorded with the Langmuir model, and the maximum adsorption capacity was 423.73 mg g⁻¹. The reaction mechanism of Cr(VI) is adsorption and redox reaction. In addition, NMC-0.50 exhibit high selectivity, separability and regeneration performance. A convenient means for the synthesis of NMC was designed in this work, and demonstrate that NMC has practical value as an adsorbent.

A biofilm reactor was designed with flat ceramic substrates to remove Co(II), Ni(II) and Zn(II) from industrial wastewater. The ceramics were made of clay and nano-rubber with high mechanical resistance. The surface of the ceramic substrate was modified with neutral fiber and nano-hydroxyapatite. A uniform and stable biofilm mass of 320 g with 2 mm of thickness was produced on the modified ceramic after 3 d. The micro-organisms were identified in the biofilm by polymerase chain reaction (PCR) method. Functional groups of biofilms were identified with a Fourier transform infrared spectrometer (FT-IR). Experiments were designed by central composite design (CCD) using the responsive surface method (RSM). The biosorption process was optimized at pH = 5.8, temperature = 22 °C, feed flux of heavy metal wastewater = 225 ml, substrate flow = 30 ml, and retention time = 7.825 h. The kinetic data was analyzed by pseudo first-order and pseudo second-order kinetic models. Isotherm models and thermodynamic parameters were applied to describe the biosorption equilibrium data of the metal ions on the biofilm-ceramic. The maximum biosorption efficiency and capacity of heavy metal ions were about 72% and 57.21 mg, respectively.

This study investigates reaction pathways for the formation of pre-PXDD/F intermediates via a radical/molecule mechanism. Thermodynamic and kinetic parameters for the combination reactions of 2-bromophenol (2-BP) and 2-chlorophenol (2-CP) precursors with key radical species including the phenoxy radicals, the phenyl radicals and the phenoxyl diradicals were calculated in detail. The couplings of phenoxy radicals with 2-B(C)P tend to produce pre-PXDD intermediates of halogenated o-phenoxyphenol. The combinations of phenyl and phenoxyl diradicals with 2-B(C)P produce two types of structures, i.e., dihydroxybiphenyl and o-phenoxyphenyl, which exclusively act as prestructures of PXDFs. These condensation reactions, especially those involving the phenyl C atom sites in phenyl and phenoxyl diradicals, are proven to be both thermodynamically and kinetically favorable and are nearly comparable with the corresponding steps involved in the radical/radical reactions. Most importantly, reactions of phenyl and phenoxyl diradicals with halogenated phenols solely lead to the formation of PXDFs, which to some extent provides a plausible explanation for the high PXDF-to-PXDD ratios in the real environment. Therefore, our study reveals the pivotal role of the radical/molecule mechanism in homogeneous gas-phase PXDD/F formation, especially in PXDF formation. The present results fill in a knowledge gap that has hitherto existed regarding dioxin formation and improve our understanding of PXDD/F formation characteristics in the environment.