A green alga, Chlamydomonas reinhardtii, was used to verify whether a simple Biotic Ligand Model (BLM) could be used to predict carefully controlled short-term biouptake for the lanthanide, Nd. In the absence of ligands or competitors, Nd biouptake was well described by a Michaelis-Menten equation with an affinity constant, KNd, of 10⁶.⁸ M⁻¹ and a maximum internalization flux of Jₘₐₓ = 1.70 × 10⁻¹⁴ mol cm⁻² s⁻¹. For bi-metal mixtures containing Nd and Ca, Mg, Sm or Eu, Nd uptake could also be well modelled by assigning experimentally determined affinity constants of KCₐ = 10².⁶ M⁻¹, KMg = 10³.⁴ M⁻¹, KSₘ = 10⁶.⁵ M⁻¹ and KEᵤ = 10⁶.⁵ M⁻¹. The similar values of Kₘ and Jₘₐₓ for the three rare earth elements (REEs): Sm, Eu and Nd is consistent with them sharing a common metal uptake site. On the other hand, in the presence of the small organic ligands (citric or malic acid), neither, free or total Nd concentrations could be used to quantitatively predict Nd internalization fluxes. In other words, in order to predict biouptake by simple BLM determinations, it was necessary to consider that the Nd complexes were bioavailable. The data strongly suggest that risk evaluations of the REE will require a new paradigm and new tools for evaluating bioavailability.

Better understanding of the colloidal behaviors of nanomaterials impacted by aquatic chemistry parameters is needed for appropriate evaluation of the environmental risks posed by nanomaterials in natural waters. In the study, the colloidal stability of Fe3O4 magnetic nanoparticles (Fe-MNPs) was evaluated over a range of chemistry characteristics [e.g., pH, dissolved organic matter (DOM), salt types, cationic strength] in six synthetic water samples. The findings from the synthetic water samples were further examined with eight “real world” environmental water samples. Our results demonstrated that DOM fraction, humic acid (HA), promoted suspension of Fe-MNPs more by hydrophobic interactions in addition to ligand exchange and electrostatic effects compared with fulvic acid (FA). Capability of cations to increase aggregation of Fe-MNPs were in the order of Ca2+ > Mg2+ >> Na+ because of their different degrees of bridging complexation with DOM molecules on particle surfaces. As a key parameter for indicating Fe-MNPs colloidal stability, Zeta (ζ) potentials of Fe-MNPs in these waters samples were well correlated to (R2 = 0.880, P < 0.001) the contents, types and adsorption forms of DOM and cations. However, several other factors could also affect the hydrodynamic diameter (HDD) of Fe-MNPs in the “real world” environmental waters. It assumed that ampholytic-DOM molecules such as amino acid- and protein-like molecules caused great aggregation of Fe-MNPs. These findings would be helpful for better understanding and evaluating the colloidal behaviors of nanomaterials when they released into natural water environment, thus could shed light on developing relevant pollution control strategies.

The main objectives of this study were to evaluate global uncertainty in the prediction of Distribution coefficients (Kds) for several Trace Metals (TM) (Cd, Cu, Pb, Zn) through the probabilistic use of a geochemical speciation model, and to conduct sensitivity analysis in speciation modeling in order to identify the main sources of uncertainty in Kd prediction. As a case study, data from the Loire river (France) were considered. The geochemical speciation model takes into account complexation of TM with inorganic ligands, sorption of TM with hydrous ferric oxides, complexation of TM with dissolved and particulate organic matter (i.e. dissolved and particulate humic acids and fulvic acids) and sorption and/or co-precipitation of TM to carbonates. Probability Density Functions (PDFs) were derived for physico-chemical conditions of the Loire river from a comprehensive collection of monitoring data. PDFs for model parameters were derived from literature review. Once all the parameters were assigned PDFs that describe natural variability and/or knowledge uncertainty, a stepwise structured sensitivity analysis (SA) was performed, by starting from computationally ‘inexpensive’ Morris method to most costly variance-based EFAST method. The most sensitive parameters on Kd predictions were thus ranked and their contribution to Kd variance was quantified. Uncertainty analysis was finally performed, allowing quantifying Kd ranges that can be expected when considering all the sensitive parameters together.

We conducted an exposure experiment with Diffusive Gradients in Thin- Films (DGT), fathead minnow (Pimephales promelas), and yellow lampmussel (Lampsilis cariosa) to estimate bioavailability and bioaccumulation of Cu. We hypothesized that Cu concentrations measured by DGT can be used to predict Cu accumulation in aquatic animals and alterations of water chemistry can affect DGT's predict ability. Three water chemistries (control soft water, hard water, and addition of natural organic matter (NOM)) and three Cu concentrations (0, 30, and 60 μg/L) were selected, so nine Cu-water chemistry combinations were used. NOM addition treatments resulted in decreased concentrations of DGT-measured Cu and free Cu ion predicted by Biotic Ligand Model (BLM). Both hard water and NOM addition treatments had reduced concentrations of Cu ion and Cu-dissolved organic matter complexes compared to other treatments. DGT-measured Cu concentrations were linearly correlated to fish accumulated Cu, but not to mussel accumulated Cu. Concentrations of bioavailable Cu predicted by BLM, the species complexed with biotic ligands of aquatic organisms and, was highly correlated to DGT-measured Cu. In general, DGT-measured Cu fit Cu accumulations in fish, and this passive sampling technique is acceptable at predicting Cu concentrations in fish in waters with low NOM concentrations.

This study presents a combination of dispersive liquid-liquid-solidified floating organic drop microextraction (DLLSFODM) and slotted quartz tube (SQT) with conventional flame atomic absorption spectrometry (FAAS) to improve the sensitivity for cadmium determination. A ligand namely 2-(4-methylphenyl)-1H-imidazo-[4,5-f]-[1,10]-phenanthroline which has not been used in trace analyte determination was used to form a cadmium complex. Stepwise optimization of parameters affecting complex formation (pH, ligand, and buffer solution) and extraction (extraction and dispersive solvents, salt effect and mixing) was done to maximize cadmium absorbance. The slotted quartz tube was fitted onto the flame burner and optimized to increase residence time of atoms in the flame. Instrumental parameters such as sample and fuel flow rate were also optimized to further enhance the absorbance signal for cadmium. Using optimal parameters and values, the limits of detection and quantification were determined to be 0.81 and 2.69 μg L⁻¹, respectively. Low percent relative standard deviations (< 6.0%) indicated good precision for both extraction and instrumental measurements. Recovery tests were used to determine the accuracy of the method and the recovery results obtained were between 88 and 113%. Graphical Abstract ᅟ

Calix[4]arene-crown-6 compounds are promising ligands in the removal of cesium. With this aim, a macrocyclic compound, calix[4]arene-crown-6, was chemically immobilized onto inorganic ordered mesoporous carbon material. Several adsorption parameters such as nitric acid concentration, contact time, initial cesium content, operation temperature, and competing ions were studied. The results demonstrated the prepared material conserved high cesium selectivity of calix[4]arene-crown-6 and physicochemistry stability of the ordered mesoporous carbon matrix and showed the superior cesium adsorption performance. The optimum adsorption acidity determined as 3.0 M nitric acid was consistent with the actual acidity value in the back-end of the nuclear fuel cycle. The Langmuir model indicated the monolayer coverage adsorption and the highest mass adsorption capacity was calculated as 128.06 mg cesium/g. The pseudo-second-order model and D-R model proved the adsorption was a chemical process. Thermodynamics parameters showed the adsorption was spontaneous and exothermal in nature. Competing ions hardly affected cesium adsorption. Furthermore, the adsorbent showed almost intact adsorption capacity after five adsorption-elution cycles. The comprehensive performance highlights the composite material as a promising adsorbent for cesium adsorption from wastewaters. Graphical Abstract

Novel magnetic ion-imprinted polymer was prepared by use of SBA-15 as functional monomer, ethylene glycol dimethacrylate as cross linker, diphenylcarbazide as ligand, and Cd²⁺, Cu²⁺, and Ni²⁺ as the template of ion source. The adsorption capacity of the synthesized adsorbent was 111, 95, and 87 mg g⁻¹, respectively for cadmium, copper, and nickel. The selectivity of the adsorbents examined in the presence of different cations including Na⁺, K⁺, Ca²⁺, Mg²⁺, Zn²⁺, Co²⁺, Fe²⁺, Mn²⁺, Hg²⁺, and Pb²⁺ indicated that the synthesized ion-imprinted adsorbents were highly selective for the appropriate cations. Kinetic studies indicated that the adsorption process was very fast and the equilibrium was established within 5 min and followed the pseudo-second-order kinetic model. The used ion-imprinted adsorbent was readily regenerated by elution with 2 M HNO₃, and the regenerated adsorbent retained most of its initial capacity. The calculated thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic.

Paddy field soil contaminated by cadmium may produce cadmium-contained corns causing Itai-itai disease, and in situ washing of soil with the organic acid is a good technical choice due to its convenience and cost-effectiveness. While the bottleneck of this technique is how to recycle the huge volume of washing effluent in an efficient and economical way. Biosorption of cadmium on the garlic peel was attempted in present study and it was found quite satisfactorily effective to remove all cadmium from the real soil leaching effluent after three-time sequential adsorption. The systematical investigation on the effect of various parameters on the adsorption of cadmium on garlic peel in the existence of tartaric ligand was performed and it was found that tartrate could change Cd²⁺ into Cd(tar)⁰ species whose electrical charge state would restrain its approach to the adsorbent particles. The porous microstructure in the transversal surface of garlic peel and the abundant groups of −COOH are the main factors affecting the adsorption capability. A demonstrative flowsheet of soil remediation by chemical washing coupled with biosorption was proposed correspondingly, in which the cadmium could be recovered from the soil washing effluent, and the recovered effluent was reused for next soil washing, and recovered garlic peel was reused for cadmium adsorption from the effluents again, showing a great prospect in the remediation of paddy field soil contaminated by cadmium. Garlic peel was used to remove the cadmium from the soil washing effluent

Mercury (Hg), one of the most toxic substances in nature, has long been released during the anthropogenic activity. A correct description of the adsorptive behavior of mercury is important to gain a better insight into its fate and transport in natural mineral surfaces, which will be a prerequisite for the development of surface complexation model for the adsorption processes. In the present study, simulation experiments on macroscopic Hg(II) sorption by gibbsite (α-Al(OH)₃), a representative aluminum (hydr)oxide mineral, were performed using the charge distribution and multi-site complexation (CD-MUSIC) approach with 1-pK triple plane model (TPM). For this purpose, several data sets which had already been reported in the literature were employed to analyze the effect of pH, ionic strength, and co-exisiting ions (NO₃⁻ and Cl⁻) on the Hg(II) adsorption onto gibbsite. Sequential optimization approach was used to determine the acidity and asymmetric binding constants for electrolyte ions and the affinity constants of the surface species through the model simulation using FITEQLC (a modified code of FITEQL 4.0). The model successfully incorporated the presence of inorganic ligands at the dominant edge (100) face of gibbsite with consistent surface species, which was evidenced by molecular scale analysis. The model was verified with an independent set of Hg(II) adsorption data incorporating carbonate binding species in an open gibbsite-water system.

Anthracite is a natural inorganic-organic hybrid environmentally friendly material, which often is used as a filter medium in water treatment. In this study, we processed anthracite particles using potassium hydroxide (KOH) with different concentrations. The anthracites, before and after treatments, were characterized by Brunauer-Emmett-Teller analysis, scanning electron microscopy, Fourier transform infrared spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy, and Boehm titration. The specific surface area and the amount of total alkalinity of anthracite were 23.73 m² g⁻¹ and 0.38 mmol g⁻¹ (increased by 101 and 217%, respectively) for 4 M KOH treatments, but decreased to 10.09 m² g⁻¹ and 0.12 mmol g⁻¹ for 10 M KOH treatments. We selected 4 M KOH-modified anthracite particles to remove 17α-ethinylestradiol (EE2) and bisphenol A (BPA) from water with unmodified anthracite used in control experiments. The pseudo-second-order model fitted well for the whole adsorption process, and intraparticle diffusion was not the unique rate-controlling step. The equilibrium adsorption data fitted well with the Langmuir-Freundlich model, and the adsorption capacities of EE2 and BPA on anthracite particles after 4 M KOH treatments were 0.7914 and 0.4327 mg g⁻¹ (increased by 138 and 97%, respectively), because the active sites markedly increased. The ligand exchange, hydrogen bonds, and π-π electron donor-acceptor interactions were the main adsorption mechanisms. The 4 M KOH-modified anthracite could be promising in large-scale applications, both as filter medium and adsorbent for organic contaminants.