Optimization of Pt(II) and Pt(IV) Adsorption from a Water Solution on Biochar Originating from Honeycomb Biomass.

Novel CO2- and H3PO4-modified biochars were successfully synthesized from raw honeycomb biomass. They were characterized via several instrumental techniques. The optimal Pt(II) and Pt(IV) adsorption onto the studied biochars was reached for the initial pH of 1.5 and a contact time of 5 min (Pt(II)) and 24-48 h (Pt(IV)). The highest static adsorption capacities for Pt(II) and Pt(IV) were obtained for the H3PO4-modified biochar: 47 mg g-1 and 35 mg g-1, respectively. The Freundlich model described the Pt(II) adsorption isotherms onto both materials and the Pt(IV) adsorption isotherm onto the CO2-activated material, and the Langmuir model was the best fitted to the Pt(IV) adsorption isotherm onto the H3PO4-activated biochar. The best medium for the quantitative desorption of the Pt form from the H3PO4-modified biochar was 1 mol L-1 thiourea in 1 mol L-1 HCl. The adsorption mechanism of both the studied ions onto the synthesized H3PO4-modified biochar was complex and should be further investigated. The H3PO4-modified biochar was successfully applied for the first time for Pt(IV) removal from a spent automotive catalyst leaching solution.

The Removal of Arsenic and Its Inorganic Forms from Marine Algae-A Base for Inexpensive and Efficient Fertilizers.

Newly synthesized cerium oxide was successfully obtained by the hard templating route. The optimal As(III) and As(V) adsorption onto the studied adsorbent was reached for the initial pH of 4.0 and a contact time of 10 h. The highest static adsorption capacities for As(III) and As(V) were 92 mg g-1 and 66 mg g-1, respectively. The pseudo-second-order model was well fitted to the As(III) and As(V) experimental kinetics data. The Langmuir model described the As(III) and As(V) adsorption isotherms on synthesized material. The adsorption mechanism of the studied ions onto the synthesized cerium oxide was complex and should be further investigated. The optimal solid-liquid ratio during the proposed aqueous extraction of inorganic As from the Fucus vesiculosus algae was 1:50. The optimal dosage of the synthesized cerium oxide (0.06 g L-1) was successfully applied for the first time for inorganic As removal from the aqueous algal extract.

Adsorption and desorption of heavy metals by the sewage sludge and biochar-amended soil.

The goal of the study was to evaluate the application of biochar (BC) to the sewage sludge (SL) on the adsorption and desorption capacity of Cd(II), Cu(II), Ni(II) and Zn(II). The effect of biochar contribution in the sewage sludge (2.5, 5 and 10%) was investigated. The isotherms data were fitted to the Langmiur (LM), Freundlich (FM) and Temkin (TM) models. The best fitting for kinetic study was obtained for the pseudo-second-order equation. The best fitting of the experimental data was observed for the LM in the case of SL and BC, and for the FM in the case of SL- and SL/BC-amended soil. SL was characterized by even four-order higher sorption capacity than BC. The addition of the BC to the SL and next to the soil increased the adsorption capacity of the soil and the SL-amended soil. In the case of all investigated potentially toxic elements (PTEs), the highest adsorption capacity was achieved for SL-amended soil in comparison with the control soil. In the case of other experimental variants, the adsorption capacity of metal ions was as follows: 2.5% BC > 5.0% BC > 10% BC. The negative correlation between hydrated radius of metal ions and the kinetics of sorption was observed. However, the desorption of PTEs from BC/SL-amended soil was significantly lower than for SL-amended soil (except of Cd) and non-amended soil. It can be concluded that the addition of the biochar enhanced the immobilization of PTEs and reduced their bioavailability and mobility in the soil amended by the sewage sludge.

An ion-imprinted thiocyanato-functionalized mesoporous silica for preconcentration of gold(III) prior to its quantitation by slurry sampling graphite furnace AAS.

A gold(III)-imprinted thiocyanato-functionalized silica network of type SBA-15 was prepared by co-condensation of tetraethoxysilane (TEOS) with thiocyanatopropyltriethoxysilane (TCTES) in the presence of Pluronic123 and Au(III) ions. Compared to the non-imprinted material, the imprint has a higher selectivity and adsorption capacity for Au(III). The maximum static adsorption capacity for Au(III) is 475 mg·g-1 for the ion-imprinted, and 62 mg·g-1 for the non-imprinted sorbent. The imprint was applied to the sorption of Au(III) from digested geological samples prior to its determination by graphite furnace atomic absorption spectrometry. Adsorption is fast and does not substantially prolong the analytical procedure. Under optimum conditions, the detection limit for Au(III) is 2 ng·g-1. The method was validated by analyzing certified reference materials, and results were in good agreement with certified values. The procedure was successfully applied to the separation and determination of gold in complex geological samples. Graphical abstract Schematic presentation of the preparation of ion-imprinted thiocyanato-functionalized mesoporous silica and its application for the preconcentration of gold from digested soils before its determination by slurry sampling graphite furnace atomic absorption spectrometry (GF AAS).

Synthesis of biochar from residues after biogas production with respect to cadmium and nickel removal from wastewater.

The objective of the study was to investigate the ability of biochars prepared under different temperatures (400 °C and 600 °C) from the residue of biogas production (RBP) for the adsorption of cadmium (Cd(II)) and nickel (Ni(II)) ions from aqueous solution. Furthermore, the RBP biochars adsorption capacity was compared with adsorption capacity of biochar produced from wheat straw at 600 °C (BCS600). The kinetics of the adsorption, the sorption isotherms, the influence of solution pH and the interfering ions (chlorides and nitrates) were investigated. The desorption of Cd(II) and Ni(II) by hydrochloric and nitric acid from biochars was also investigated. The different types of feedstock used for biochar (BC) preparation (RBP and biomass) determined the physico-chemical properties of biochars and hence their adsorption abilities. Generally, biochars produced from RBPs (regardless of temperature) had the greater capacity to adsorb Cd(II) and Ni(II) than the biochar produced from wheat straw. Of the tested models (Freundlich and Langmuir), the Langmuir model was demonstrated to be the best to describe the sorption of Cd(II) and Ni(II). For the kinetic study, the adsorption process proceeded the fastest for BCU400 than BCU600. Furthermore, BCU600 was the most resistant to the influence of interfering ions on adsorption. For the desorption study, BCU400 was characterized by the highest reproducibility of the surface. The comparison of the results obtained in each adsorption step between RBP biochars and BCS600 suggested that the residue from biogas production could be successfully applied for the removal of Cd(II) and Ni(II) ions from aqueous solutions.

Determination of bismuth in environmental samples by slurry sampling graphite furnace atomic absorption spectrometry using combined chemical modifiers.

Slurry sampling graphite furnace atomic absorption spectrometry technique was applied for the determination of Bi in environmental samples. The study focused on the effect of Zr, Ti, Nb and W carbides, as permanent modifiers, on the Bi signal. Because of its highest thermal and chemical stability and ability to substantially increase Bi signal, NbC was chosen as the most effective modifier. The temperature programme applied for Bi determination was optimized based on the pyrolysis and atomization curves obtained for slurries prepared from certified reference materials (CRMs) of the soil and sediments. To overcome interferences caused by sulfur compounds, Ba(NO3)2 was used as a chemical modifier. Calibration was performed using the aqueous standard solutions. The analysis of the CRMs confirmed the reliability of the proposed analytical method. The characteristic mass for Bi was determined to be 16 pg with the detection limit of 50 ng/g for the optimized procedure at the 5% (w/v) slurry concentration.

Determination of Fluorine by Ion-Selective Electrode and High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry with Respect to Animal Feed Safety.

Fluorine, depending on its concentration and chemical form, is essential or toxic to humans and animals. Therefore, it is crucial to be able to determine it reliably. In this study, fluorine was determined in animal feed after extraction with HCl (gastric juice simulation). The standard potentiometric method with a fluoride-selective electrode (ISE) and newly developed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GFMAS) method was applied. Feed samples turned out to be a challenge for HR-CS GFMAS. Chemical interferences (formation of competing molecules, CaF, GaCl, and GaP, instead of the target GaF molecule) and spectral effects (including a phosphorous molecule spectrum and atomic lines) were identified. An additional difficulty was caused by reagent contamination with F and memory effects. Difficulties were eliminated/reduced. The quality of ISE analysis was multi-directionally verified (including comprehensive proficiency testing). A risk of inaccuracy at low F concentration, where the calibration relationship is nonlinear, was investigated. The results of both methods were consistent, which confirms the accuracy of the methods and informs that the extracted fluorine is in fluoride form. The results of extensive ISE tests conducted in Poland in 2021-2023 have shown that, in most cases, the fluoride content is significantly lower than the threshold values.

Modified Ordered Mesoporous Carbons for Cr(VI) Removal from Wastewater.

The pristine CMK-3 carbon was ozonized and then chemically modified by the Zr and Fe compounds. The synthesized carbonaceous materials were characterized with physicochemical methods. The obtained carbons had a high specific surface area (ca. 800 m2 g-1) and an acidic surface. The Cr(VI) adsorption properties of the oxidized and Zr/Fe-modified carbon were studied. The highest static adsorption capacity towards Cr(VI) ions was evaluated for Zr/Fe-modified carbon (50.1 mg g-1) at pHeq = 5.8 after 240 min. The Elovich and Freundlich theoretical models were well fitted to the Cr(VI) adsorption kinetic and isotherm data on the Zr/Fe-modified CMK-3-type carbon. The leading Cr(VI) adsorption mechanism acting on the Zr/Fe-modified carbon was probably based on the redox reactions between Cr(VI) and the carbonaceous surface. Electrostatic attraction and surface complexation processes could also occur during Cr(VI) adsorption in the studied system. The effect of the competitive anions on the concentration level, such as in the galvanic wastewater for Cr(VI) adsorption onto chemically modified carbon, was negligible. The HCl and HNO3 media were insufficient for the Zr/Fe-modified carbon regeneration after Cr(VI) adsorption. The Zr/Fe-modified carbon was successfully applied for the efficient (>90%) Cr(VI) removal from the model galvanic wastewater.

Diclofenac-Impregnated Mesoporous Carbon-Based Electrode Material for the Analysis of the Arsenic Drug Roxarsone.

This paper describes a novel electrode material, diclofenac-impregnated mesoporous carbon modified with a cationic surfactant, cetyltrimethylammonium bromide (DF-CMK-3/CTAB), for ultratrace analysis of the arsenic drug roxarsone (ROX). DF-CMK-3 amorphous carbon is a material with a high specific surface area and well-defined, hexagonally ordered, thin mesopores. The functional groups attached to the carbonaceous surface, such as chromene and pyron-like oxygen groups, lactam, and aromatic carbon rings, have the basic character and they can donate electrons. Modification of DF-CMK-3 with a CTAB layer significantly increases the analytical signal due to electrostatic interactions between the cationic surfactant and the anion form of ROX in the acidic medium. The voltammetric procedure at the glassy carbon sensor modified with DF-CMK-3/CTAB exhibited excellent sensitivity (limit of detection of 9.6 × 10-11 M) with a wide range of linearity from 5.0 × 10-10 to 1.0 × 10-4 M. Analysis of real samples (treated municipal wastewater and river water) showed recoveries from 96 to 102% without applying the complicated sample pretreatment step. The sensor demonstrated excellent sensitivity in the analysis of the arsenic drug ROX in the presence of interferences in environmental water samples.

Modified Mesoporous Carbon Material (Pb-N-CMK-3) Obtained by a Hard-Templating Route, Dicyandiamide Impregnation and Electrochemical Lead Particles Deposition as an Electrode Material for the U(VI) Ultratrace Determination.

In this paper, a dicyandiamide-impregnated mesoporous carbon (N-CMK-3), electrochemically modified in situ with lead film (Pb-N-CMK-3), was tested as an electrode material for U(VI) ultratrace determination. The prepared carbon material was characterized by XRD, SEM-EDX, Raman, FT-IR, XPS analysis and nitrogen sorption measurements. The changes of electrochemical properties of glassy carbon electrodes (GCE) after the N-CMK-3 and Pb-N-CMK-3 modification were studied using CV and EIS methods. The modification of the GCE surface by the N-CMK-3 material and Pb film increases the electroactive area of the electrode and decreases the charge transfer residence and is likely responsible for the electrochemical improvement of the U(VI) analytical signal. Using square-wave adsorptive stripping voltammetry (SWAdSV), two linear calibration ranges extending from 0.05 to 1.0 nM and from 1.0 to 10.0 nM were observed, coupled with the detection and quantification limits of 0.014 and 0.047 nM, respectively. The Pb-N-CMK-3/GCE was successfully applied for U(VI) determination in reference materials (estuarine water SLEW-3 and trace elements in natural water SRM 1640a).

The effect of pH and ageing on the fate of CuO and ZnO nanoparticles in soils.

The objective of this study was to evaluate the fractionation of ZnO and CuO engineered nanoparticles (ENPs) in soils with a pH adjusted to 4.0, 6.5, and 9.0 after 1 day and 30 days of incubation. Based on the multi-stage extraction, 5 fractions of metals were determined. Moreover, the effect of ENPs on the activity of acid, neutral and alkaline phosphatase was determined. The results of the study revealed that pH had a dominant effect on the metal participation in soils. The levels of those fractions of metals differed between nano-ZnO and nano-CuO, which could have resulted from differences in the dissolution of the ENPs. After 1 day, the concentration of Zn2+ (0.02-7.4 mg L-1) was 10 times higher than that of Cu2+. The metal fractionation in soil treated with ENPs and metal salts may also confirm the role of ENP dissolution. The concentration of potentially bioavailable fraction of Zn increased with a drop in pH. At a 4 pH concentration of Zn in the treatment with nano-ZnO and ZnCl2 was at a similar level (42.1-45 mg kg-1), whereas the addition of nano-CuO resulted in a lower content of Cu (24.7 mg kg-1) than CuCl2 (36.5 mg kg-1). On the other hand, the concentration of fraction exchangeable of both metals in the alkaline soil did not exceed the level of 5.0 mg kg-1. Sample incubation time was especially important for metal participation in samples with a pH of 6.5. The greatest differentiation of metal fractionation between the soils was also noted at a pH of 6.5, which could also have been a result of other properties of the soils. The strong effect of pH on the lability of ENPs in soils confirmed a need to trace the fate of ENPs in extreme soil conditions as well as in changing environment.

Tailoring Surface Chemistry of Sugar-Derived Ordered Mesoporous Carbons Towards Efficient Removal of Diclofenac From Aquatic Environments.

Ordered mesoporous carbon (CMK-3), obtained from an abundant natural source, sugar, was thermochemically modified with dicyandiamide and thiourea as well as by classical oxidization with hydrogen peroxide to introduce specific surface groups. Thermochemical modifications resulted in carbon with almost unchanged porosity and altered surface chemistry while porosity of H2O2-treated carbon was seriously deteriorated. The obtained carbons were tested as sorbents of diclofenac, considered as one of the emerging water contaminants. Changes in porosity and surface chemistry of modified carbons resulted in significant differences with regard to the uptake of diclofenac. Dicyandiamide-modified carbon showed highest uptake of drugs, reaching 241 mg g-1 that is attributed to its developed microporosity as well as surface chemistry composed of basic groups facilitating electrostatic interactions with diclofenac anions. Desorption study showed that diclofenac is strongly bonded, albeit with a different degree depending on the modification of the CMK-carbon. The obtained results were compared with up-to-date literature regarding sorption of diclofenac by carbon-based sorbents.

Antineoplastic effects of auranofin in human pancreatic adenocarcinoma preclinical models.

BACKGROUND: Auranofin, a Food and Drug Administration-approved anti-rheumatic agent with anticancer properties for lung and ovarian cancer, has never been studied for pancreatic cancer. We hypothesize that auranofin may prevent pancreatic ductal adenocarcinoma progression by inhibition of Txnrd1 and HIF-1α. METHODS: In vitro sensitivity of human pancreatic ductal adenocarcinoma cell lines was determined based on IC50. Western blot assays were used to interrogate mechanisms of apoptosis and resistance. Ex vivo live tissue slice assays of xenografts allowed for testing of a larger number of PDX samples with high efficiency. In vivo pancreatic ductal adenocarcinoma orthotopic mouse models using MiaPaCa-2 Luc + cells were designed to determine optimal dose and antitumor effect. RESULTS: We found that 10 of 15 tested pancreatic ductal adenocarcinoma cell lines were sensitive to auranofin based on IC50s below 5 µmol/L. Ex vivo tissue growth inhibition greater than 44% was observed for 13 PDX tissue cases treated with 10 µmol/L auranofin. High Txnrd1 expression was observed for resistant cell lines. In vivo studies showed 15 mg/kg IP as the optimal dose with absence of gross solid organ metastasis up to 13 weeks post-treatment (median survival 8 and 12 weeks, respectively; P = .0953). CONCLUSIONS: We have demonstrated that auranofin prevents pancreatic ductal adenocarcinoma progression using multiple models. Our study suggests inhibition of Txnrd1 and HIF-1α as possible mechanisms of action, and Txnrd1 as a biomarker of resistance. Based on these data, an off-label Phase 0 clinical trial with this FDA-approved drug should be considered for patients with pancreatic cancer.

Studies of cadmium(II), lead(II), nickel(II), cobalt(II) and chromium(VI) sorption on extracellular polymeric substances produced by Rhodococcus opacus and Rhodococcus rhodochrous.

The adsorption of Cd(II), Pb(II), Ni(II), Co(II) and Cr(VI) ions on the extracellular polymeric substances (EPS) obtained from bacterial strain Rhodococcus opacus and Rhodococcus rhodochrous was investigated by the static sorption method. Influence of pH, time and temperature were studied. It was found that the influence of the pH value and time of adsorption depends on the type of adsorbed ions. For all investigated systems an increase of temperature above 35°C reduces adsorption. However, the static sorption capacities values oscillate around 1.5mmol/g, independently of the type of the studied metal ions. The adsorption mechanism of studied metal ions onto the tested EPSs seems to be very complex and it is probably due to an electrostatic attraction, a surface complex formation and chemical interaction between the metal ions and the functional groups (mainly hydroxyl, acetamido or amino groups) of bacterial extracellular biopolymers.

Sorption and desorption of Cr(VI) ions from water by biochars in different environmental conditions.

In the present research, the potential of two biochars produced by the thermal decomposition of wheat straw (BCS) and wicker (BCW) for Cr(VI) ions removing from wastewater was investigated. The pH and the presence of chlorides and nitrates were also investigated. The Freundlich and Langmuir models were applied for the characterization of adsorption isotherms. The Langmuir model has better fitting of adsorption isotherms than the Freundlich model. The sorption process can be described by the pseudo second-order equation. The optimal adsorption capacities were obtained at pH 2 and were 24.6 and 23.6 mg/g for BCS and BCW, respectively. X-ray photoelectron spectroscopy (XPS) studies confirmed that Cr(III) ions were the most abundant chromium species on the biochars' surface. The results indicated that the sorption mechanism of Cr(VI) on biochar involves anionic and cationic adsorption combined with Cr(VI) species reduction.

Application of laboratory prepared and commercially available biochars to adsorption of cadmium, copper and zinc ions from water.

The goal of the presented work was the evaluation and comparison of two biochars (produced from Sida hermaphrodita - BCSH/laboratory produced and from wheatstraw - BCS/commercial available) to adsorb heavy metal ions (Cd(II), Cu(II) and Zn(II)) from water. Kinetics of the sorption as well as sorption isotherms, the influence of solution pH and interfering ions were investigated. Different physico-chemical properties of biochars had the great influence on adsorption capacity. The greater adsorption efficiency was observed for BCSH than for BCS in the case of all investigated metals. The adsorption efficiency of BCSH was correlated with higher content of carbon and oxygen, what is equal with higher content of polar-groups on the BCSH surface e.g., -COOH. Furthermore, the molar ratio of O/C as well as polarity index (which was higher for BCSH) was also important parameters.

Preparation and evaluation of Fe-loaded activated carbon for enrichment of selenium for analytical and environmental purposes.

The adsorbent, based on the thermal modification of activated carbon impregnated by iron(III) nitrate(V), has been prepared and applied for selenium enrichment from aqueous solution. Various ratios of the impregnating agent to carbon mass were carefully examined with respect to selenium adsorption capacity and selectivity. The basic Se(VI) ions adsorption parameters affecting the adsorption ability onto the prepared activated carbons were studied. The carbon impregnated by 10% Fe(NO(3))(2) and thermally treated at 200 °C possessed the highest adsorption capacity and selectivity towards selenium ions. The physico-chemical characterization of the prepared adsorbents before and after selenium uptake were carried out using scanning electron microscopy (SEM) equipped with an energy dispersive X-ray detector (EDX) and X-ray photoelectron spectroscopy (XPS). The studies confirmed the surface complexation reactions of iron species and selenium on the Fe-loaded activated carbon. Due to its high adsorption capacity enrichment of selenium on the studied adsorbent has been successfully applied for its determination in the complementary feeds, using the carbon slurry sampling graphite furnace atomic absorption spectrometry technique (GFAAS) and standard calibration method.

Determination of vanadium in soils and sediments by the slurry sampling graphite furnace atomic absorption spectrometry using permanent modifiers.

A new analytical procedure for vanadium (V) determination in soils and sediments by the slurry sampling graphite furnace atomic absorption spectrometry (slurry sampling GFAAS) using the mixed permanent modifiers is described. Moreover, the comparison of action of the modifiers based on the iridium (Ir) and carbide-forming elements: tungsten (W) and niobium (Nb) deposited on the graphite tubes is studied, especially in terms of their analytical utility and determination sensitivity. The mechanism of their action was investigated using an X-ray diffraction technique (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray detector (EDX). Finally, the mixture of 0.3 µg of Ir and 0.04 µg of Nb was used for the graphite tube permanent modification. The analytical procedure was optimized on the basis of the data from pyrolysis and atomization temperature curves studies. The results obtained for the four certified reference materials (marine sediments: PACS-1 and MESS-1, lake sediment: SL-1, soil: San Joaquin Soil SRM 2709), using the slurry sampling GFAAS and the standard calibration method, were in good agreement with the certified values. The detection and quantification limits and characteristic mass calculated for the proposed procedure were 0.04 µg/g, 0.16 µg/g and 11.9 pg, respectively. The precision (RSD% less than 8%) and the accuracy of vanadium determination in the soil and sediment samples were acceptable.

Chromium determination in food by slurry sampling graphite furnace atomic absorption spectrometry using classical and permanent modifiers.

A simple method, using permanent modifiers, has been developed for chromium (Cr) determination in food of plant origin by the slurry sampling graphite furnace atomic absorption spectrometry. In particular comparison of the action of Mg(NO3)2, iridium (Ir)/niobium (Nb) and iridium (Ir)/tungsten (W) was examined. Finally, for chromium determination in food, the mixture of 2µg of Ir with 10µg of Nb was used as permanent modifier. The analytical procedure was optimised carefully on the basis of the data from pyrolysis and atomisation temperature curves studies. The results obtained for four certified reference materials using external calibration with aqueous standards were in good agreement with the certified values. The precision and accuracy of Cr determination by the described method were also acceptable: the RSD were lower than 10% and recoveries for CRMs were in the range of 95-103%. The characteristic mass for chromium was determined to be 3.9pg and the detection limit for the optimised procedure at the 0.75% (w/v) slurry concentration - 86.6ngg(-1).