Editorial - "Special Collection: 30 Years of PIP" - Physicochemistry of Interfacial Phenomena.

2023 marked the 30th anniversary of the Section of Physicochemistry of Interfacial Phenomena (PIP) of the Polish Chemical Society (PCS). It was established in 1993 on the initiative of members of the Lublin Branch of PCS. On May 18 the same year, the Chairman of the Branch, Prof. Roman Leboda asked the President of the Management Board of PCS to register a new section, called Physical Chemistry of Surface Phenomena. Prof. Wladyslaw Rudzinski was elected for the chairman of the Section, who is a world-renowned specialist in the field of adsorption. In May 1994, the inaugural meeting of the founding members of the Section took place in Kazimierz Dolny, Poland. The aim of it was presentation of the research topics of scientists representing various centers and teams that are part of Section. On June 10, 1997, at one of the subsequent meetings in Kraków, its members unanimously decided to change the name to the Section of Physicochemistry of Interfacial Phenomena.

Removal of Organic Dyes, Polymers and Surfactants Using Carbonaceous Materials Derived from Walnut Shells.

A series of new granular carbonaceous adsorbents was prepared via single-stage physical and chemical activation of walnut shells. Their suitability for removing various types of organic pollutants (represented by dyes, surfactants and water-soluble polymers) from the liquid phase was assessed. The activation of the precursor was carried out with CO2 and H3PO4 using conventional heating. Activated biocarbons were characterized in terms of chemical composition, acidic-basic nature of the surface, textural and electrokinetic properties as well as thermal stability. Depending on the type of activating agent used during the activation procedure, the obtained biocarbons differed in terms of specific surface area (from 401 to 1361 m2/g) and the type of porous structure produced (microporosity contribution in the range of 45-75%). Adsorption tests proved that the effectiveness of removing organic pollutants from the liquid phase depended to a large extent on the type of prepared adsorbent as well as the chemical nature and the molecular size of the adsorbate used. The chemically activated sample showed greater removal efficiency in relation to all tested pollutants. Its maximum adsorption capacity for methylene blue, poly(acrylic acid), poly(ethylene glycol) and Triton X-100 reached the levels of 247.1, 680.9, 38.5 and 61.8 mg/g, respectively.

Research on Green Adsorbents.

Adsorption processes play a crucial role in air purification, wastewater treatment, soil remediation technologies, noble metals recovery, and long-term energy storage systems [...].

Investigation of Ionic Polymers' Stabilizing and Flocculating Properties in Dispersed Activated Carbons Systems.

Activated carbons obtained via the thermochemical treatment of lemon balm and mint herbs were applied for ionic polymers adsorption, which directly affects the stability of these types of aqueous suspensions. The examined carbonaceous materials were characterized by well-developed specific surface area (approximately 1000 m2/g) and mesoporous structure. The adsorbed amounts of anionic poly(acrylic acid) and cationic polyethyleneimine from one-component solutions reached significant levels, but the efficiency of adsorption of these compounds from binary solutions slightly decreased. Moreover, the ionic polymers showed stabilizing properties towards the activated carbons suspensions. For both adsorbents, the most stable suspensions were systems containing both types of polymeric macromolecules with different ionic characters. This was due to the occurrence of electrosteric and depletion stabilization mechanisms. Furthermore, the zeta potential and size of particle aggregates were also influenced by the presence of polymers in the aqueous suspensions of activated carbons.

Preparation of biochars by conventional pyrolysis of herbal waste and their potential application for adsorption and energy purposes.

The nettle, sage, mint and lemon balm herbs were used for biochars preparation. The physicochemical parameters of obtained materials were related to the lignocellulose composition of the precursors. It has been proved that the content of mineral substance has a significant influence on development of surface area, whereas the amount of hemicellulose affects the content of surface functional groups. It has been also shown that the obtained biochars are characterized by great energy parameters. The higher heating values (HHV) of the carbonaceous materials are comparable to the typical energy sources. The greatest HHV value (20.36 MJ/kg) was characteristic for the biochar obtained by pyrolysis of the lemon balm. In addition, the biochars were used for ionic polymers adsorption from one- and two-components solutions. Despite the adsorbed amounts of macromolecules are not great is has been proved that polyethylenimine and polyacrylic acid have positive influence on their mutual adsorption.

Adsorption of Organic Pollutants on Carbonaceous Adsorbents Prepared by Direct Activation of Sweet Cherry Stones.

The main objective of this study was to assess the usefulness of the sweet cherry stones for the production of carbonaceous adsorbents by means of direct physical activation method, using conventional and microwave variant of heating. The adsorbents were characterized in terms of textural parameters, acidic-basic character of the surface, electrokinetic properties and their suitability for drinking water purification. Adsorption tests were carried out against three organic compounds - Triton X-100 (surfactant), bovine serum albumin (protein) and methylene blue (synthetic dye). Depending on the variant of heating applied during activation procedure, the obtained activated biochars differed significantly in terms of the elemental composition, acidic-basic properties as well as degree of specific surface development and the type of porous structure generated. Adsorption tests have showed that the efficiency of organic pollutants removal from aqueous solutions depends significantly not only on the type of the adsorbent and adsorbate applied, but also on the temperature and pH of the system. The sample prepared by microwave-assisted direct activation proved to be very effective in terms of all tested organic pollutants adsorption. The maximum sorption capacity toward Triton X-100, bovine serum albumin and methylene blue reached the level of 86.5, 23.4 and 81.1 mg/g, respectively.

Production of Mineral-Carbon Composites and Activated Carbons as a Method of Used Gear Oil, Ashes, and Low-Quality Brown Coals Management.

The main objective of this study was to assess the usefulness of the low-quality brown coal, ash obtained as a result of its combustion, as well as used gear oil for the production of mineral-carbon adsorbents. The adsorbents were characterized in terms of textural parameters, acidic-basic character of the surface, mineral matter contribution to the structure, as well as their suitability for drinking water purification. Adsorption tests were carried out against two synthetic dyes-methylene blue and methyl orange. In order to understand the nature of the organic pollutants adsorption, the effect of the initial dye concentration, temperature, and pH of the system as well as the phase contact time were investigated. The obtained mineral-carbon composite and activated carbons significantly differed not only in terms of the elemental composition and chemical character of the surface (from slightly acidic to strongly alkaline), but also showed a very diverse degree of specific surface development (from 21 to 656 m2/g) and the type of porous structure generated (from micro/mesoporous to typically mesoporous). Adsorption tests showed that the efficiency of organic dye removal from aqueous solutions primarily depends on the type of the adsorbent and adsorbate applied, and, to a lesser extent, on the temperature and pH of the system. In turn, kinetic studies have shown that the sorption of dyes on such materials is consistent with a pseudo-second-order kinetics model, regardless of the type of adsorbed dye.

The Influence of Oxidation and Nitrogenation on the Physicochemical Properties and Sorption Capacity of Activated Biocarbons Prepared from the Elderberry Inflorescence.

The main objective of the study was to prepare a series of new activated biocarbons by means of physical and chemical activation of elderberry inflorescence. The influence of carbon matrix nitrogenation/oxidation on the physicochemical properties and sorption abilities of the carbonaceous materials was investigated. The impact of initial dye concentration, pH and temperature of the system on methylene blue and rhodamine B removal efficiency was checked. It was shown that activation of elderberry inflorescences with CO2 or H3PO4, and their further modification by introducing nitrogen or oxygen functional groups, allowed us obtain a wide range of materials that differ significantly in terms of the chemical nature of the surface, degree of specific surface development and the type of porous structure generated. The samples prepared by chemical activation proved to be very effective in terms of cationic dyes adsorption. The maximum sorption capacity toward methylene blue and rhodamine B reached the level of 277.8 and 98.1 mg/g, respectively. A better fit to the experimental data was achieved with a Langmuir isotherm than a Freundlich one. It was also shown that the efficiency of methylene blue and rhodamine B adsorption from aqueous solutions decreased with increasing temperature of the system.

Carbon Adsorbents Obtained from Pistachio Nut Shells Used as Potential Ingredients of Drinking Water Filters.

Water resources are increasingly degraded due to the discharge of waste generated in municipal, industrial and agricultural areas. Therefore, the search for new materials enabling the effective treatment of drinking water and sewage is currently of great interest. This paper deals with the adsorption of organic and inorganic pollutants on the surface of carbonaceous adsorbents prepared by thermochemical conversion of common pistachio nut shells. The influence of the direct physical activation with CO2 and chemical activation with H3PO4 on parameters, such as elemental composition, textural parameters, acidic-basic character of the surface as well as electrokinetic properties of the prepared carbonaceous materials was checked. The suitability of the activated biocarbons prepared as the adsorbents of iodine, methylene blue and poly(acrylic acid) from the aqueous solutions was estimated. The sample obtained via chemical activation of the precursor turned out to be much more effective in terms of all the tested pollutants adsorption. Its maximum sorption capacity toward iodine was 1059 mg/g, whereas in relation to methylene blue and poly(acrylic acid) 183.1 mg/g and 207.9 mg/g was achieved, respectively. For both carbonaceous materials, a better fit to the experimental data was achieved with a Langmuir isotherm than a Freundlich one. It has also been shown that the efficiency of organic dye, and especially anionic polymer adsorption from aqueous solutions, is significantly affected by solution pH and temperature of the adsorbate-adsorbent system.

Movements of a Specialist Butterfly in Relation to Mowing Management of Its Habitat Patches.

Over the centuries, mowing and grazing have been crucial for sustaining populations of grassland insects and their overall diversity in Europe. While long-term positive effects of mowing have been studied in more detail, little is known about the direct impacts of mowing on adult butterflies. Here, we explore how different habitat management (mown, recovered after mowing and unmown) affects movements and population estimates of the endangered specialist butterfly Phengaris teleius. The results showed higher dispersal probability from mown (22%) and recovered meadows (16%) than from the unmown ones (9%). However, mowing shortened the average dispersal distances (mown = 102 m, recovered = 198 m, unmown = 246 m) and reduced butterfly population size. In contrast, a larger area of the habitat patches promoted long-distance dispersal and sustained larger populations. We hypothesise that mowing caused depletion of resources and triggered dispersal of poorly adapted individuals. This behaviour is maladaptive and could lead to higher dispersal-related mortality; thus, mowing should be avoided before and during the butterfly flight period. This study suggests that the species' persistence in a fragmented landscape depends on large, unmown and interconnected habitats that support more viable populations, promote long-distance dispersal, and enable (re)colonisation of vacant patches.

Production of Activated Carbons from Food/Storage Waste.

This paper deals with the adsorption of organic and inorganic pollutants on the surface of carbonaceous adsorbents prepared via the chemical activation of expired or broken food products-the solid residue of the "cola-type" drink as well as spoilt grains of white rice and buckwheat groats. The activation process was conducted in the microwave furnace with the use of two activating agents of different chemical nature-potassium carbonate and orthophosphoric acid. The activated carbons were characterized based on the results of elemental analysis, low-temperature nitrogen adsorption/desorption, Boehm titration, thermal analysis, and scanning electron microscopy. Additionally, the suitability of the materials prepared as the adsorbents of methylene blue and iodine from the aqueous solutions was estimated. The materials obtained via chemical activation with H3PO4 turned out to be much more effective in terms of both model pollutant adsorptions. The maximum sorption capacity toward iodine (1180 mg/g) was found for the white-rice-based activated carbon, whereas the most effective in the methylene blue removal (221.3 mg/g) was the sample obtained from the solid residue of the expired "cola-type" drink. For all carbonaceous materials, a better fit for the experimental adsorption data was obtained with the Langmuir isotherm model than the Freundlich one.

Accumulation of toxic Pb(II) ions by the iron-containing minerals in the presence of ionic polyacrylamide soil conditioner.

The aim of this research was to determine the adsorption-desorption, surface, electrokinetic, and stability properties of aqueous suspensions of iron-containing minerals in the presence of anionic polyacrylamide (AN PAM) and lead(II) ions. Three minerals found in the soil environment, akaganeite, goethite, and magnetite, were synthesized based on the precipitation method. The interaction mechanism of heavy metal ions with polymer flocculant, which are adsorbed on the soil mineral particles, was proposed. It was shown that the best affinity to the AN PAM or/and Pb(II), adsorbed both from single and mixed solution, shows akageneite (characterized by the highly developed specific surface area). Polymer-metal complexes formed in the mixed adsorbate systems are rather stable, evidence of which is reduced desorption and consequently limited bioavailability of toxic lead ions for organisms and plants in soil environment.

Biochars and Activated Biocarbons Prepared via Conventional Pyrolysis and Chemical or Physical Activation of Mugwort Herb as Potential Adsorbents and Renewable Fuels.

The main objective of this study was to prepare a series of biochars and activated biocarbons via conventional pyrolysis as well as chemical or physical activation of solid residue after solvent extraction of wild growing plant (popular weed)-mugwort. The influence of the variant of the thermochemical treatment of the precursor on such parameters as elemental composition, textural parameters, acidic-basic character of the surface as well as adsorption abilities of the prepared carbonaceous materials was checked. Moreover, the suitability of the biochars prepared as renewable fuels was also investigated. It has been shown that the products obtained from the mugwort stems differ in many respects from the analogous materials obtained from mugwort leaves. The products were micro/mesoporous materials with surface area reaching 974.4 m2/g and total pore volume-1.190 cm3/g. Surface characterization showed that chemical activation with H3PO4 results in the acidic character of the adsorbents surface, whereas products of pyrolysis and especially physical activation show strongly alkaline surface properties. All the adsorbents were used for methylene blue and iodine adsorption from the aquatic environment. To understand the nature of the sorption process, the Langmuir, Freundlich and Temkin isotherm models were employed. The Langmuir model best described the experimental results, and the maximum sorption capacity calculated for this model reached 164.14 mg of methylene blue per gram of adsorbent. In case of iodine removal, the maximum capacity reached 948.00 mg/g. The research carried out for the biochars prepared via conventional pyrolysis showed that the value of their heat of combustion varies in the range from 21.74 to 30.27 MJ/kg, so they can be applied as the renewable fuels.

Simultaneous Removal of Polymers with Different Ionic Character from Their Mixed Solutions Using Herb-Based Biochars and Activated Carbons.

Nettle and the sage herbs were used to obtain carbonaceous adsorbents. For the biochar preparation the precursors were dried and subjected to conventional pyrolysis. Activated carbons were obtained during precursor impregnation with phosphoric(V) acid and multistep pyrolysis. The textural parameters and acidic-basic properties of the obtained adsorbents were studied. The activated carbons prepared from the above herbs were characterized by the largely developed specific surface area. The obtained carbonaceous adsorbents were used for polymer removal from aqueous solution. Poly(acrylic acid) (PAA) and polyethylenimine (PEI) were chosen, due to their frequent presence in wastewater resulting from their extensive usage in many industrial fields. The influence of polymers on the electrokinetic properties of activated carbon were considered. PAA adsorption caused a decrease in the zeta potential and the surface charge density, whereas PEI increased these values. The activated carbons and biochars were used as polymer adsorbents from their single and binary solutions. Both polymers showed the greatest adsorption at pH 3. Poly (acrylic acid) had no significant effect on the polyethylenimine adsorbed amount, whereas PEI presence decreased the amount of PAA adsorption. Both polymers could be successfully desorbed from the activated carbons and biochar surfaces. The presented studies are innovatory and greatly required for the development of new environment protection procedures.

Activated Biocarbons Obtained from Plant Biomass as Adsorbents of Heavy Metal Ions.

This paper deals with the adsorption of heavy metal ions on the surface of carbonaceous materials obtained via the chemical activation of biomass. Waste plum stones, pine sawdust and horsetail herb were used as the precursors of carbonaceous adsorbents. The effect of the precursor type and preparation procedure on the physicochemical properties of activated biocarbons and their sorption abilities towards Pb(II) and Cu(II) ions have been checked. The obtained micro-mesoporous activated biocarbons were characterized by determination of elemental composition and ash content, the number of surface functional groups and pH of water extracts as well as textural study based on low temperature nitrogen adsorption/desorption and scanning electron microscopy. Additionally, the electrokinetic studies including solid surface charge density and zeta potential determination were performed. Moreover, the adsorption data modelling (equilibrium and kinetics), XPS results analysis and comparison of parameters characterizing electrical double layer formed at the solid-liquid interface enabled the specification of the mechanism of heavy metals binding with the activated biocarbons surface. The maximum adsorption capacity towards copper and lead ions (177.5 and 178.1 mg/g, respectively) was found for plum stone-based activated biocarbon. For all carbonaceous materials, better fit to the experimental data was achieved with a Langmuir isotherm than a Freundlich one. In turn, a better fit of the kinetics data was obtained using the pseudo-second order model.

Pseudogap in underdoped cuprate seen in longitudinal magnetoresistance.

We report the results of in-plane magnetotransport study of slightly underdoped cuprate La1.85Sr0.15CuO4(LSCO15) with Ni impurity. Increasing Ni contentycauses a sharp drop in longitudinal magnetoresistance (LMR) in LSCO15 to broaden and move towards higher temperatures. TemperatureTmLMR(y)of this local maximum in LMR coincides with temperatureTdev(y), below which ideal resistivity from the parallel-resistor model deviates from itsT2-dependence. A direct comparison with the hole doping evolution of pseudogap (PG) in La2-xSrxCuO4(LSCO), possible through the mobile-carrier concentration extracted from the thermopower measurements, allows to equate both characteristic temperaturesTmLMR≅Tdevwith PG opening temperatureT∗. The rate of PG closing by magnetic field parallel to the CuO2plane, in measurements up to 9 T, is consistent with spin-paramagnetic effect in this configuration and yields PG closing fieldBpcclose to the second critical fieldBc2predicted for superconducting gap with the help of Werthamer-Helfand-Hohenberg theory. The field anisotropy ofBpcsuggests that orbital degrees of freedom also play a role in PG formation.

Biochars and activated carbons as adsorbents of inorganic and organic compounds from multicomponent systems - A review.

Biochars are obtained by biomass pyrolysis, whereas activated carbon is a biochar that has undergone chemical or physical activation. Owing to the large surface area and easy surface modification both solids are widely applied as adsorbents. They are low-costs materials, they could be regenerated and their disposal is not troublesome. Adsorption of heavy metals, dyes, pharmaceuticals on the surface of biochars and activated carbons, from simple systems of adsorbate containing only one compound, are described extensively in the literature. The present paper provides an overview of reports on adsorption of inorganic and organic compounds onto these two types of adsorbents from the mixed adsorbate systems. The described adsorbate systems have been divided into those consisting of: two or more inorganic ions, two or more organic compounds and both of them (inorganic and organic ones). The research of this type is carried out much less frequently due to the more complicated description of interactions in the mixed adsorbate systems.

Removal of Organic Dyes from Aqueous Solutions by Activated Carbons Prepared from Residue of Supercritical Extraction of Marigold.

In the present work, we reported on the efficiency of the removal of organic dyes by adsorption on activated carbons prepared from the residue of supercritical extraction of marigold. The performance of adsorbents prepared was tested towards methyl red, methylene blue, malachite green, and crystal violet at room temperature. The effects of carbonization (500 and 700 °C) and activation (700 and 800 °C) temperatures, textural parameters, and acid-base character of the adsorbent surface on the sorption properties of the activated carbons were established. Activated carbons are characterized by low developed specific surface area, from 2 to 206 m2/g, and have a basic character of the surface (pH of carbons water extracts ranging from 10.4 to 11.2). Equilibrium adsorption isotherms were investigated. The equilibrium data were analyzed in the Langmuir, Freundlich, and Temkin models. The adsorption capacities of activated carbons studied varied from 47.62 to 102.43 mg/g towards methyl red, 53.14 to 139.72 mg/g towards methyl red, 425.46 to 622.80 towards malachite green and 155.91 to 293.75 mg/g towards crystal violet, from their water solutions. Kinetics of the adsorption of the organic dyes studied were found to be described by the pseudo-second-order model. It was proven that through the physical activation of the residue of supercritical extraction of marigold, it is possible to obtain carbonaceous materials of very high adsorption capacity towards organic pollutants.

Intersexual Differences in Behaviour and Resource Use of Specialist Phengaris teleius Butterflies.

Although the behaviour of the Large Blue butterflies of the genus Phengaris (= Maculinea) is relatively well studied, most empirical data come from investigations of their dispersal and oviposition. Here, we assessed overall intersexual differences in resource use by tracking Phengaris teleius (Bergsträsser, 1779) individuals and recording the duration of their behaviours. Females were characterised by frequent, short flights, and devoted more time to resting and oviposition. Males engaged in numerous, but usually short interactions, and spent most of the time in flight exploring their surroundings for receptive females. Their average flight time was significantly longer compared to females. Average feeding time did not differ between the sexes but was shorter when butterflies were feeding on Sanguisorba officinalis L. Intraspecific interactions within P. teleius were three times longer than those with other insect species, and interactions between sexes were particularly long lasting. Significantly shorter interspecific interactions imply that butterflies can easily recognise conspecifics and differentiate between sexes, which offers obvious fitness benefits. Both sexes, but especially females, showed strong association with their larval host plant, and less so with other flowers of similar colour and shape. Females predominantly used their host plant for feeding, which possibly indicates neuro-sensory constraints towards this resource.