Thermodynamic Solution Properties of a Biodegradable Chelant (L-glutamic-N,N-diacetic Acid, L-GLDA) and Its Sequestering Ability toward Cd2+

The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect was also interpreted in terms of the formation of weak complexes between the ligand and the cations of supporting electrolytes, resulting in a greater tendency of GLDA to chemically interact with Na+ rather than K+ and, in turn, (CH3)4N+. Formation constants of GLDA with Cd2+ were determined in NaCl(aq) at different ionic strength values. Five complex species were found, namely CdL2−, CdHL−, CdH2L0(aq), Cd2L0(aq), and Cd(OH)L3−, whose formation constant values at infinite dilution were log β = 12.68, 17.61, 20.76, 17.52, and 1.77, respectively. All the species results were relevant in the pH range of natural waters, although the Cd2L0(aq) was observed only for CCd ≥ CGLDA and concentrations of >0.1 mmol dm−3. The sequestering ability of GLDA toward Cd2+, evaluated by means of pL0.5, was maximum at pH~10, whereas the presence of a chloride containing a supporting electrolyte exerted a negative effect. Among new generation biodegradable ligands, GLDA was the most efficient in Cd2+ sequestration.The authors C.B., P.C., A.I., G.L. and C.D.S. thank the University of Messina for the Research and Mobility 2017 Project (cod. 009041). Authors thank COST action CA18202—Network for Equilibria and Chemical Thermodynamics Advanced Research for the support to this study. O.G.-L. is grateful to the project IT-742-13 for Consolidated Research Groups, funded by the Basque Country Government, for her post-doctoral contract

Non-Invasive Approach to Investigate the Mineralogy and Production Technology of the Mosaic Tesserae from the Roman Domus of Villa San Pancrazio (Taormina, Italy)

The archaeological excavations at Villa San Pancrazio (Taormina, Italy) are bringing to light a vast Roman-Imperial residential quarter featuring luxurious dwellings decorated with wall paintings and mosaic floors, pointing it out as one of the most significant archaeological sites of the city. The polychrome and black and white mosaics recovered date back to the middle Imperial period, during the 2nd century AD. This work deals with the first archaeometric investigations of the materials employed for the tesserae production with the aim of elucidating the mineralogical composition and obtaining analytical evidence that can contribute to extracting information related to their production technology. For that purpose, a non-invasive methodology, based on micro energy dispersive X-ray fluorescence (μ-EDXRF) spectrometry and Raman spectroscopy, was used to characterize a wide selection of stone, ceramic and glass tesserae. Chemometric tools were exploited to manage the large set of elemental data collected on black and white lithic samples, providing essential clues for the subsequent investigations. The results evidenced the employment of natural lithotypes (calcareous sedimentary, dolomitic and volcanic) local and imported, and also artificial materials, such as ceramic made firing magnesium-rich clays, soda-lime-silica glasses made with different opacifying and coloring agents (such as calcium antimoniate, cobalt and copper)This work was supported by project IT-742-13 for Consolidated Research Groups, funded by the Basque Country Government. P. Irizar gratefully acknowledges his predoctoral grant (PRE2018-085888) from the MINECO Spanish Ministry. O. Gómez-Laserna is grateful to the University of the Basque Country (UPV/EHU) for her postdoctoral contract. P. Cardiano also thanks University of Messina (FFABR UNIME 2020) for funding

Experimental study and modelling of inorganic Cd2+ speciation in natural waters

Environmental contextCadmium(II) is considered as one of the most dangerous pollutants in natural waters. We performed a complete study on the interactions of cadmium(II) with inorganic components of natural waters, by using new experiments and some literature data. The body of results can be considered an improvement in modelling the inorganic speciation of cadmium(II) in natural waters. AbstractAn analysis of literature data together with new potentiometric and voltammetric studies on the interaction between Cd2+ and the common environmental inorganic ligands, such as OH–, Cl–, F–, CO32– and SO42–, was reported at t = 25°C. New formation constant values for CdCl+, CdCl20, CdCl(OH)0, CdSO40, CdCO30 and CdF+ species at different ionic strengths (0.1 ≤ I ≤ 1 mol L–1) were determined. The cumulative seawater ligand capacity was evaluated by using a model in which synthetic seawater is expressed as a single salt BA, where the major cations (Na+, K+, Ca2+ and Mg2+) are represented by a single cation Bz+ and the anions (Cl– and SO42–) by a single anion Az– (|z| = 1.117). The formation of CdA0.883+ and CdA(OH)0.117– species was proposed and formation constants are reported at different salinities (5 ≤ S ≤ 45). The ionic strength dependence of the stability constants was studied by means of Pitzer and SIT (Specific ion Interaction Theory) equations

Understanding the Solution Behavior of Epinephrine in the Presence of Toxic Cations: A Thermodynamic Investigation in Different Experimental Conditions

The interactions of epinephrine ((R)-()-3,4-dihydroxy--(methylaminomethyl)benzyl alcohol; Eph) with dierent toxic cations (methylmercury(II): CH3Hg+; dimethyltin(IV): (CH3)2Sn2+; dioxouranium(VI): UO22+) were studied in NaClaq at dierent ionic strengths and at T = 298.15 K (T = 310.15 K for (CH3)2Sn2+). The enthalpy changes for the protonation of epinephrine and its complex formation with UO22+ were also determined using isoperibolic titration calorimetry: DHHL = 39 1 kJ mol1, DHH2L = 67 1 kJ mol1 (overall reaction), DHML = 26 4 kJ mol1, and DHM2L2(OH)2 = 39 2 kJ mol1. The results were that UO22+ complexation by Eph was an entropy-driven process. The dependence on the ionic strength of protonation and the complex formation constants was modeled using the extended Debye–Hückel, specific ion interaction theory (SIT), and Pitzer approaches. The sequestering ability of adrenaline toward the investigated cations was evaluated using the calculation of pL0.5 parameters. The sequestering ability trend resulted in the following: UO2 2+ >> (CH3)2Sn2+ > CH3Hg+. For example, at I = 0.15 mol dm3 and pH = 7.4 (pH = 9.5 for CH3Hg+), pL0.5 = 7.68, 5.64, and 2.40 for UO22+, (CH3)2Sn2+, and CH3Hg+, respectively. Here, the pH is with respect to ionic strength in terms of sequestration

Spectroscopic measurements of the pH in NaCl brines

Spectrophotometric measurements of the pH in natural waters such as seawater have been shown to yield precise results. In this paper, the sulfonephthalein indicator m-cresol purple ( mCP, H 2I) has been used to determine the pH of NaCl brines. The indicator has been calibrated in NaCl solutions from 5 to 45 °C and ionic strengths from 0.03 to 5.5 m. The calibrations were made using TRIS buffers (0.03 m, TRIS/TRIS–HCl) with known dissociation constants pK TRIS in NaCl solutions [Foti C., Rigano C. and Sammartano S. (1999) Analysis of thermodynamic data for complex formation: protonation of THAM and fluoride ion at different temperatures and ionic strength. Ann. Chim. 89, 1–12]. The values of pH were determined from pH = pK m CP + log { ( R - e 1 ) / ( e 2 - Re 3 ) } where R = 578 A/ 434 A, the ratios of the indicator absorbance maximum at 578 and 434 nm, e 1 = 0.00691, e 2 = 2.222 and e 3 = 0.1331 [Clayton T. and Byrne R. H. (1993) Spectrophotometric seawater pH measurements: total hydrogen ion concentration scale calibration of m-cresol purple and at-sea results. Deep-Sea Res. 40, 2115–2129]. Measurements were also made in NaCl solutions with different levels of TRIS (0.01–0.11 m). At low levels of TRIS buffer (<0.03 m), the values of pK m CP increased significantly. This effect can lead to erroneous values of pK m CP at low ionic strengths in estuaries and lakes. The measured values of pK m CP in NaCl as a function of ionic strength ( I/m) and temperature ( T/K) were fitted to the equation ( σ = 0.0072) pK m CP = - 29.095 + 2639.2 / T + 5.0417 ln T - 0.3307 I 0.5 - 186.80 I 0.5 / T - 0.28346 I + 296.44 I / T + 0.12841 I 1.5 - 68.23 I 1.5 / T These results should be useful in determining the pH of NaCl brines in natural waters from 0 to 50 °C

Prediction of water solubility and Setschenow coefficients by tree-based regression strategies

The experimental determination of water solubility (log S 0 ) and Setschenow coefficient (k m ) of a compound is a time-consuming activity, which often needs large amounts of expensive substances. This work aims at establishing two \u201copen-source\u201d chemometric models based on a regression tree that is able to predict the two abovementioned quantities. The dataset used is the largest to appear up to now for the collection of k m values, containing information on 295 molecules and it is relevant also for the collection of logS 0 values (321 molecules); for each of them 32 descriptors were taken from freely available databases. Information about water solubility and Setschenow coefficients, necessary to train the models, were taken from available literature. Validation was performed on a separate test set of molecules. The precision reached in the prediction is fully satisfying, being RMSEP = 0.6086 and 0.0441 for logS 0 and k m , respectively

A novel thermodynamic approach for the complexation study of toxic metal cations by a landfill leachate

Landfill leachates can contaminate nearby aquifers. The hazards deriving from this contamination also depend on the chemical speciation of various contaminants. A novel approach is proposed here to face this problem from a chemical thermodynamics point of view. The complexing ability of the soluble fraction of a landfill leachate (collected from Bellolampo, Palermo, Italy) towards Pb2+, Cd2+and Cu2+has been investigated at T = 298.15 K in NaClaqat I = 0.1 mol dm-3. The soluble fraction of the landfill leachate was first characterized by different analytical techniques. Then, its acid-base properties were studied by ISE-H+potentiometric titrations and modelled by the so-called diprotic-like model. Differential Pulse Anodic Stripping Voltammetry (DP-ASV) titrations of metal ion aqueous solutions with a diluted landfill leachate were carried out, successively, in order to determine the stability constants of the leachate-metal complexes. The stability of the Pb2+/OH-and Pb2+/Cl-complexes was also studied by the same technique. Finally, the sequestering ability of the leachate towards the investigated metal cations has been quantified by the calculations of various pL0.5values under different pH conditions. The results proved that the landfill leachate is a good sequestering agent toward those cations, reducing the fraction of the free cations in solution, and that it can be a selective sequestrant at different pH

Modelling the dependence on medium, ionic strength and temperature of N-acetyl-L-cysteine acid-base properties, and its interactions with Na+, Mg2+, Ca2+ and Zn2+

N-acetyl-L-cysteine (NAC) is the acetylated precursor of L-cysteine, and it is strictly related to glutathione activity. NAC is used in medicine since more than 30 years, primarily as a mucolytic, though its properties are exploited in the treatment of many diseases, such as acute poisoning by acetaminophen (restoring protective levels of glutathione), HIV, contrast-induced nephropathy, type-2 DM (diabetes mellitus), and it also looks promising in the treatment of several psychiatric disorders [1]. This resulted in a huge number of scientific contributions published during the years on NAC (searching in some scientific databases, more than 10000 papers appear). As expected, most of them are focused on the biological and therapeutic activity of NAC, while relatively few data are reported on the solution chemistry of this molecule, despite the thorough knowledge of its acid-base and coordination behaviour are of fundamental importance for the understanding of its properties in aqueous solution, as biological fluids are. Moreover, the relatively few thermodynamic data available (necessary to assess the speciation of this ligand in the system under study) are reported in single, specific conditions, while it is well known that the most of biological fluids (and natural waters) are, from a chemico-physical perspective, multielectrolyte aqueous solutions of very variable composition, ionic strength, and temperature [2]. Therefore, in this contribution we report the results of an investigation on the modelling of the acid-base properties of NAC in different ionic media (sodium and tetramethylammonium chlorides and tetraethylammonium iodide) at different ionic strengths (0 < I / mol dm-3 ≤ 3.0) and temperatures (283.15 ≤ T / K ≤ 318.15). Due to their importance from a biological perspective, we also report the results on the binding ability of NAC towards Na+, Mg2+, Ca2+ and Zn2+ in NaClaq at T = 298.15 K and different ionic strengths (0 < I / mol dm-3 ≤ 2.0). Surprisingly, despite the importance of these cations and their involvement in many biological mechanisms strictly connected with NAC activity, to our knowledge almost no data (only some for Zn2+) are present in literature on these interactions. The dependence on medium, ionic strength and temperature of the protonation and complex formation constants obtained has been modelled by classical approaches, such as the Extended Debye-Hückel (EDH), Specific ion Interaction Theory (SIT), Pitzer, and by the van’t Hoff equation

Sequestering ability of landfill leachate towards toxic metal ions

The great part of municipal solid wastes is worldwide stored in sanitary landfills. The interaction of organic and inorganic wastes with rainwater produces in the landfill a leachate of extremely variable composition. It depends on several variables such as the type of wastes, the age of landfill, the pH, the redox potential, etc [1-2]. Four are the recognized categories of pollutants in landfill leachate: inorganic macrocomponents, dissolved organic matter (DOM), heavy metals and xenobiotic organic compounds [3]. In particular, heavy metals (arsenic, cadmium, copper, lead, mercury, etc.) are usually present at concentration of few ppb and up to some ppm. A variable but consistent fraction of DOM is constituted by humic and fulvic-like compounds, formed through a series of biological and chemical processes that involve DOM, especially during the methanogenic phase of wastes decomposition [3]. The great number of binding sites in humic like substances, mainly carboxylic and phenolic groups, are responsible of the high sequestering ability of leachate towards metal ions. As consequence, the speciation scheme of all the toxic metal ions contained in the landfill is strictly influenced by the amount and composition of DOM fraction in leachate. Due to the imperfections or the possible damages of landfill liners, the leachate can contaminate superficial and ground waters in proximity of the landfill causing serious environmental pollution and human health risks. In a previous study the presence and the amount of landfill leachate, also in trace, on some groundwater samples collected in proximity of Bellolampo landfill was evaluated [4]. The obtained results showed a leachate concentration of ~ 130 μg L-1. Landfill of Bellolampo is a solid waste sanitary landfill near Palermo (Sicily). The landfill has been created in 1960s and become a controlled dump site in 1980s. Previous ICP-OES measurements on Bellolampo leachate have been shown a Pb, Cd and Cu concentrations in the ranges 0.05 - 2.3, 0.02 - 0.12 and 0.02 - 0.6 mg L-1 respectively. The environmental and health risks related to the presence of toxic heavy metal ions in leachate depends on the species that metals form with the other components and at the conditions of the contaminated groundwater, with particular attention to the amount of free metal ions, the most dangerous among their possible species in aqueous solution. For this reason, the study of the sequestering ability of landfill leachate towards toxic metal ions is of fundamental importance to establish the environmental impact of leachate contamination. Here we present a potentiometric and voltammetric (Differential Pulse Anodic Stripping Voltammetry, DP-ASV) study on the acid-base properties and on the sequestering ability of leachate samples collected in Bellolampo landfill towards Cd(II), Pb(II) and Cu(II) ions. The voltammetric and potentiometric titrations were carried out in NaCl aqueous solution, at I = 0.1 mol L-1 in order to simulate the mean experimental conditions typical of groundwaters. The acid – base properties of the filtered leachate were compared to those of the soluble fraction of humic substances, with carboxylic and phenolic groups as main binding sites of the macromolecules. Two units namely leach1 and leach2 containing COOH and phenol OH groups, respectively were considered and the Diprotic Like model has been used to process the ISE-H+ potentiometric data [5]. The voltammetric titrations of toxic metal ions solutions with leachate (diluted or as it is) were carried out adjusting the pH of titrand solutions at 5. The results shown an appreciable sequestering ability of leachate towards the heavy metal ions considered and an estimation of the metal complexes stability has been done by calculating rough metal – leachate formation constants