0000000000928314

AUTHOR

Antonio Gianguzza

Capacità sequestrante di acido alginico e fulvico nei confronti di composti di triorganostagno(IV)

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PAHs composition of surface sediments of the‘Stagnone di Marsala’ coastal lagoon in the tyrrhenian west coast of Sicily

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CADMIUM AND COPPER SORPTION ON PECTIN ENCAPSULATED IN CALCIUM ALGINATE BEADS

Pectin is an acidic polysaccharide constituted by monomer units of galacturonic acid. It is a main component of peel fruits where is present as protopectin. Due to the presence of a high number of carboxylic binding sites in its structure, pectin (Pect) shows a good sequestering capacity towards metal ions. Pectin has been proposed as a sorbent to remove metal ions from aqueous solutions. In this work the ability of pectin on solid phase to remove Cd(II) and Cu(II) from aqueous solutions has been evaluated. To this end, a powder of a commercial pectin, (esterified potassium salt from Citrus fruit) was encapsulated in a polymeric matrix of calcium alginate (CA) at different ratios of pectin …

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Sequestering ability of polyaminopolycarboxylic ligands towards dioxouranium(VI) cation

Abstract In the present paper, some results of an investigation (at t = 25 °C by potentiometry, ISE-H+ glass electrode) on the sequestering ability of five different polyaminopolycarboxylic ligands [Nitrilotriacetate (NTA), ethylenediamine-N,N,N′,N′-tetraacetate (EDTA), ethylene glycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetate (EGTA), diethylenetriamine-N,N,N′,N″,N″-pentaacetate (DTPA), triethylenetetraamine-N,N,N′,N″,N′′′,N′′′-hexaacetate (TTHA)] towards dioxouranium(VI) cation in sodium chloride aqueous solutions, at I = 0.7 mol L−1 are reported. Calculations performed on potentiometric data gave evidence of the formation of the following species (log β in parenthesis): UO2(NTA)H0 (12…

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Equilibrium Studies in Natural Fluids. A Chemical Speciation Model for the Major Constituents of Seawater.

AbstractThe speciation of CI−, OH− and SO42- in synthetic sea water has been studied by Potentiometric measurements (pH-metric and ISE-Na methods) and by literature data analysis, using a well tested complex formation model. Stability constants, together with distribution of hypothesised species in synthetic sea water, as a function of temperature and salinity, are reported. The speciation model proposed in this work is discussed on the basis of chemical and statistical considerations. Comparison with some literature sea water models is given.

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Speciation of organic matter in natural waters. Interaction of polyacrylates with the major cation components of seawater

The speciation of some high molecular weight polycarboxylates was studied in different ionic media. Polyacrylates here investigated (W=2.0, 5.1 and 20.0 kDa) form weak species with alkali metal cations (K=102 mol l1, t=25 jC, I=0 mol l1) and quite stable complexes with alkaline earth metal cations (K>106 mol l1, t=25 jC, I=0 mol l1). Results are reported from experiments performed in a multicomponent electrolyte solution simulating the major composition of seawater (artificial seawater). Protonation constants in this medium are expressed as a polynomial function of S1/2 (S=salinity) and the sharp lowering with respect to values obtained in non-interacting aqueous tetraalkylammonium salts ca…

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Monitoraggio di gas anestetici in sale operatorie di Palermo e provincia

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Sequestration of organometallic compounds by natural organic matter. binding of trimethyltin(IV) by fulvic and alginic acids

The binding capacity of fulvic and alginic acids towards trimethyl tin(IV) cation was quantitatively determined in order to evaluate the sequestering ability of toxic organometallic compounds by natural organic matter. Investigations were performed in the pH range of natural waters (5–8.5) where the carboxylate groups, largely present in both sequestering agents, are the main binding sites. A chemical interaction model, according to which both the protonation of polyelectrolyte ligands and the hydrolysis of the organotin cation in NaCl aqueous solution were considered, was used to define the speciation of the systems under investigation. Measurements performed at different ionic strength va…

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Geochemical mobility of toxic elements in soil and sedimets from Sicily

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INTERAZIONE DI COMPOSTI DI METILSTAGNO(IV) CON LEGANTI CARBOSSILICI

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Sequestering ability of some chelating agents towards methylmercury(II).

A study on the interactions between CH3Hg+ and some S, N and O donor ligands (2-mercaptopropanoic acid (thiolactic acid (H2 TLA)), 3-mercaptopropanoic acid (H2 MPA), 2-mercaptosuccinic acid (thiomalic acid (H3 TMA)), d,l-penicillamine (H2 PSH), l-cysteine (H2 CYS), glutathione (H3 GSH), N,N′-bis(3-aminopropyl)-1-4-diaminobutane (spermine (SPER)), 1,2,3,4,5,6-benzenehexacarboxylic acid (mellitic acid (H6 MLT)) and ethylenediaminetetraacetic acid (H4 EDTA)) is reported. The speciation models in aqueous solution and the possible structures of the complexes formed are discussed on the basis of potentiometric, calorimetric, UV spectrophotometric and electrospray mass spectrometric results. For t…

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Thermodynamic parameters for the formation of glycine complexes with magnesium(II), calcium(II), lead(II), manganese(II), cobalt(II), nickel(II), zinc(II) and cadmium(II) at different temperatures and ionic strengths, with particular reference to natural fluid conditions

Abstract Protonation constants and Mg 2+ , Ca 2+ , Pb 2+ , Mn 2+ -, Co 2+ , Ni 2+ , Cu 2+ , Zn 2+  and Cd 2+ glycine complex formation constants have been determined in different aqueous media at different temperatures. Salt effects are explained by a complex formation model which takes into account the formation of weak species. From the temperature dependence of the formation constants, thermodynamic parameters ΔH θ (and in some cases ΔC θ p ) have been obtained. A rigorous analysis of literature data, together with experimental findings, allows recommended formation parameters, in the ranges 0 ≤ I e ≤ 1 mol l −1 ( I e is the effective ionic strength) and 5°C ≤ T ≤ 45°C, to be obt…

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Kinetic and equilibrium studies for uranyl removal from aqueous solution by adsorption onto alginate gel beads. DPV and ICP measurements

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Sequestration of Pd2+ by polyamino-polycarboxylic ligands

The increase of the worldwide demand of “Platinum group elements” (PGE) for application in several fields such as industry, medicine, jewellery and, especially, in catalyst converter production, caused a noticeable increasing of PGE concentration in the environment. Though palladium, among the anthropogenic PGE, is not the most abundant one, it is the most hazardous since it undergoes easily and quickly oxidation to palladium(II) when in contact with soils, with a consequent increase of its mobility in the environment. The presence of complexing agents, which form soluble complex species with palladium(II), favours the mobility of the ion with an increase of its availability to plants, anim…

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Speciation of Al3+ in fairly concentrated solutions (20 to 200 mmol L-1) at I = 1 mol L-1 (NaNO3), in the acidic pH range, at different temperatures.

AbstractThe hydrolysis of Al3+ was studied in aqueous 1 mol L−1 NaNO3 solution at different concentrations (20–200 mmol L−1) and temperatures (283.15–343.15 K) by potentiometry (ISE-H+, glass electrode). Many different speciation models were considered in the calculations and it was found that the best model is represented by the following species: Al(OH)2+, Al(OH)45+, Al13(OH)327+. Hydrolysis constants and enthalpy changes at different temperatures are reported.

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Complexes of dioxouranium(VI) ion with glutamic and aspartic acids in NaCl aqueous solution

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Metals distribution in the organic and inorganic fractions of soil: A case study on soils from Sicily

The content of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, has been determined in the organic and inorganic fraction of eight soil samples from Sicily. A modified type-Tessier sequential extraction procedure has been used to recognize metals in five different fractions categorised as follows: (a) exchangeable metals, (b) metals bound to carbonates, (c) metals bound to iron and manganese oxides, (d) metals bound to organic matter, and (e) metals in residual fraction. The mineralogical composition of soils samples was characterized by X-ray diffraction. Humic substances were extracted by means of an alkaline extraction procedure. It has been found that both the mineralogical composition and the di…

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Speciation of chitosan-phosphate and chitosan-nucleotide systems in an NaCl aqueous solution

AbstractThe speciation of chitosan (310 kDa) with organic (adenosine 5’-monophosphate, AMP, and adenosine 5’-triphosphate, ATP), and inorganic phosphorus containing ligands (phosphate and pyrophosphate) was investigated in NaCl aqueous solutions at I = 0.1mol L−1 and T = 25°C. For all the systems, the investigated results obtained gave evidence for the formation of (chitosan)LHi complex species (L = nucleotides, phosphate and pyrophosphate; i = 1 to 4, but for AMP, i = 1 to 3). The stability data of complex species were used to calculate the sequestering ability of chitosan towards phosphorus compounds considered here, expressed as pL50 i.e., – log(total chitosan concentration) necessary to…

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Complexes of organometallic compounds

Abstract Novel 1/1 adducts have been obtained from the complex N , N ′-ethylenebis(salicylideneiminato)nickel(II) (NiSalen) with di- and mono-organotin(IV) chlorides, and their solid state configuration investigated by Mossbauer , IR and electronic spectroscopy and magnetic measurements. In coordinated NiSalen the square planar structure is maintained around Ni II , and the coordination to tin involves three-coordinate phenolic oxygens. The environment of Sn IV is judged to be octahedral in both types of compounds. A trans -R 2 , cis -Cl 2 configuration is advanced for R 2 SnCl 2 NiSalen.

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Hydrolysis of methyltin(IV) trichloride in aqueous NaCl and NaNO3 solutions at different ionic strengths and temperatures

The hydrolysis of methyltin(IV) trichloride (CH 3 SnCl 3 ) has been studied in aqueous NaCl and NaNO 3 solutions (0 < l/mol dm -3 ≤1), at different temperatures (15 ≤ T/°C ≤ 45) by potentiometric measurements (H + -glass electrode). By considering the generic hydrolytic reaction pCH 3 Sn 3+ + qH 2 O = (CH 3 Sn) p (OH) q 3p-q +qH + (logβ pq ), we have the formation of five species and logβ 12 = -3.36, logβ 13 = -8.99, logβ 14 = -20.27 and logβ 25 = -7.61. The first hydrolysis step is measurable only at very low pH values and was not determined: a rough estimate of the hydrolysis constant is logβ 11 = -1.5 (± 0.5). The dependence on ionic strength of logβ pq is quite different in NaNO 3 and N…

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LEAD(II) AND CADMIUM(II) REMOVAL FROM AQUEOUS SOLUTIONS USING HAZELNUT AND ALMOND SHELLS SORBENT MATERIALS

Removal of toxic metal ions from natural and waste waters is of great importance for the health of living organisms and for environmental protection. Alternatively to the conventional chemical treatments, such as precipitation, reverse osmosis, etc, biosorption shows a growing interest for toxic metal ions removal from contaminated aqueous solutions. The sorption ability of every type of biomass towards metal ions depends on many variables that characterize the solution. Among these, the ionic strength (I) is one of the most important and cannot be neglected during an accurate adsorption study. For this reason and with the aim of quantitatively define the influence of I, here are reported t…

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Palladium(II) Complexes of Aminopolycarboxylic Ligands in Aqueous Solution

Thebindingcapacityof fiveaminopolycarboxylicligands(APCs)(nitrilotriacetate(NTA),ethylenediamine-N,N,N 0 , N 0 -tetraacetate (EDTA), (S,S)-ethylenediamine-N,N 0 -disuccinic acid (S,S-EDDS), diethylenetriamine-N,N,N 0 ,N 00 ,N 00 -pentaacetate (DTPA), and triethylenetetraamine-N,N,N 0 ,N 00 ,N 000 ,N 000 -hexaacetate (TTHA)) toward the palladium(II) ion was studied by potentiometric titrations (ISE-H + electrode) in NaNO3 and in NaClO4/NaI (at different molar ratios) solutions and by spectrophotometric titrations (only in NaClO4), at I = 0.1 mol 3 kg � 1 and at T = 298.15 K. The high stability of Pd 2+ -complexones species inhibits the formation of sparingly soluble hydroxo species until pH …

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Solubility and acid-base properties and activity coefficients of chitosan in different ionic media and at different ionic strengths, at T=25°C

Studies on the acid-base properties and solubility of a polyammonium polyelectrolyte (chitosan) with different molecular weights (MW 310 and 50 kDa), were performed at T=25 °C, in the pH range 2.5–7. The protonation of chitosan was investigated by potentiometry ([H+]-glass electrode) in NaCl, NaNO3 and mixed NaNO3+Na2SO4 ionic media, at different ionic strengths. Protonation constants were calculated as a function of dissociation degree α by means of two different models, namely, a simple linear model and the modified Henderson–Hasselbalch equation. Experimental data were also fitted using a model independent of α (Diprotic-like model), according to which the acid-base properties can be sim…

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Interaction of UO2(2+) with ATP in aqueous ionic media.

Interaction of dioxouranium(VI) (uranyl) ion with ATP was studied by ligand/proton and metal/hydroxide displacement technique, at very low ionic strength and at I=0.15 mol L(-1), in aqueous Me4NCl and NaCl solutions, at t=25 degrees C. Measurements were carried out in the pH range 3-8.5, before the formation of precipitate. Computer analysis allowed us to find the quite stable species UO2(ATP)H2(0), UO2(ATP)H-, UO2(ATP)2-, UO2(ATP)2(6-), UO2(ATP)2H2(4-) and UO2(ATP)(OH)3- whose formation constants are (at I=0 mol L(-1)) logbeta(112)=18.21, logbeta(111)=14.70, logbeta(110)=9.14, logbeta(120)=12.84, logbeta(122)=24.82, and logbeta(11-1)=2.09, respectively. Different values were obtained in th…

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Organometallic complexes with biological molecues, part 3.in vivo cytotoxicity of diorganotin (IV) chloro and triorganotin (IV) chloro derivatives of penicillin g on chromosomes ofaphanius fasciatus (pisces, cyprinodontiformes)

In order to obtain a continuous source of mitotic metaphases, gill tissue of Aphaius fasciatus (Pisces, Cyprinodontiformes) has been successfully employed. Results gathered after exposure of fish to R2SnClpenG, R3SnClpenGNa, to the parents R2SnCl2, R3SnCl and to penGNa (penGNa = penicillinGNa; R = methyl, butyl and phenyl) suggest that both the parent organotin (IV) chloride and organotin (IV) chloropenG derivatives are toxic while penGNa exerts no significant toxic activity. Essentially, all of the chromosome abnormalities are classifiable as irregularly staining of chromosomes, breakages, side-arm bridges or pseudochiasmata.

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Palladium(II) sequestration by phytate in aqueous solution. Speciation analysis and ionic medium effects.

Environmental context.In the last 20 years, the demand for palladium and other platinum-group elements has intensified, causing a significant increase in their concentration in the environment, with particular accumulation in urban areas. Knowledge about Pd2+ speciation in aqueous media is fundamental for the understanding of its biological and environmental activity in contaminated areas. Phytic acid appears to be a good sequestering agent towards Pd2+ under various conditions, indicating its potential use in the remediation of contaminated sites. Abstract. Palladium(II) speciation in the presence of phytate (Phy12–) was studied by H+ ion selective electrode (ISE) potentiometry at 25°C in…

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Complex species formation of Cu and Cd metal ions with polyacrylate, polymethacrylate and alginate ligands. Potentiometric investigation by ISE-H+ and Ise-Me2+ electrodes

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Modelling S-carboxymethyl-L-cysteine protonation and activity coefficients in NaClaq and (CH3)4NClaq by SIT and Pitzer equations

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Chemical speciation of nucleotide 5′-monophosphates in the presence of biogenic amines

The interaction of adenosine-, uridine-, inosine- and guanosine-5’-monophosphates with protonated ethylenediamine, putrescine, cadaverine, spermidine and spermine, was studied potentiometrically, a...

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Equilibrium studies in natural fluids: interactions of -PO43−, -P2O74−and -P3O105−with the major constituents of sea water

AbstractThe interaction of PiO(i+2)−(3i+1) (i = 1,2,3) with the major components of seawater has been studied potentiometrically, at 25°C, in an artificial seawater (Na+, K, Ca2+, Mg2+, Cl− and SO42−) at different salinities (5—45%o). Apparent protonation constants have been calculated, from potentiometric data, and estimated, using an appropriate complex formation model. Formation constants of complexes formed by phosphates and the cation of seawater (the inorganic content of seawater being considered as a single 1:1 salt) have been determined. The comparison between experimental and estimated results showed that a suitable complexation model can be used with a fairly good accuracy in pred…

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Equilibrium studies in natural waters: Speciation of phenolic compounds in synthetic seawater at different salinities

Interactions between some phenolic compounds and macro-constituents of synthetic seawater (Na{sup +}, K{sup +}, Ca{sup 2+}, Mg{sup 2+}, Cl{sup {minus}}, and SO{sub 4}{sup 2{minus}}), at 20, 35, and 45 {per_thousand} salinity, have been investigated potentiometrically by using the [H]-glass electrode. The formation constants of phenol, o- and p-cresol, o-a dn p-nitrophenol complexes with sodium, potassium, calcium, and magnesium ions have been determined in the ionic strength range 0 {le} I {le} 1 mol/L. A comparison between the apparent protonation constants of phenols determined in synthetic seawater, and those simulated by a suitable complex formation model, is discussed. The possibility …

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Capacità sequestrante di leganti poliammino policarbossilici nei confronti dello ione uranile

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Binding of synthetic and natural polycarboxylates by biogenic polyammonium cations in aqueous solution

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Salt effects on the protonation of l-histidine and l-aspartic acid: a complex formation model

Abstract Protonation constants of l -histidine (histidinate: his − ) and l -aspartic acid (aspartate: asp 2− ) were determined potentiometrically, using the (H + ) glass electrode, in aqueous tetraethylammonium iodide (Et 4 NI), calcium chloride and sodium chloride solutions, at 0 −3 and 10 ⩽, T ⩽, 45 ° C. Differences in protonation constants determined in different salt media were explained by a complex formation model and, according to this model, the presence of the following species was hypothesized: Ca(his) + , CaH(his) 2+ , CaH 2 (his) 3+ Na(his) 0 , H 3 (his)X + , H 2 (his)X 0 , Et 4 N(his) 0 , Et 4 NH(his) + , Ca(asp) 0 , CaH(asp) + , CaH 2 (asp) 2+ , Na(asp) − , NaH(asp) 0 , H 3 (a…

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Complexes of Azelaic and Diethylenetrioxydiacetic Acids with Na+, Mg2+, and Ca2+ in NaCl Aqueous Solutions, at 25 °C

Formation constants of Na + , Mg 2+ , and Ca 2+ complexes of azelaic and diethylenetrioxydiacetic acids have been determined by potentiometry (H + -glass electrode) at different ionic strengths (0 ≤ I ≤ 1 mol dm -3 ), at t = 25 °C. For all the systems the species ML and MHL have been found. The relative formation constants are reported together with the parameters for the dependence on ionic strength. Results are discussed in comparison with those for other carboxylic ligands. Speciation problems are considered also.

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The PAH composition of surface sediments from Stagnone coastal lagoon, Marsala (Italy)

Abstract This paper examines the presence, distribution, nature and sources of 22 Aromatic Hydrocarbons (PAHs), which are important environmentally and toxicologically, in sediments from the Stagnone coastal lagoon at Marsala (Italy). Analysis was performed by gas chromatography/mass spectrometry (GC/MS) with selected ion monitoring (SIM). The total concentration of polycyclic aromatic hydrocarbons ranged from 72 to 18381 μg/kg of dry matrix. The relative standard deviation (RSD) of the replicates on the concentrations of individual compounds ranged from 5% to 20%. The accuracy of method was estimated by analyzing “blank” samples added of known quantities of analytes and the recover percent…

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Speciation of trialkyltin(IV) cations in natural fluids

The hydrolysis of (CH(3))(3)Sn(+), (C(2)H(5))(3)Sn(+) and (C(3)H(7))(3)Sn(+) has been studied in a Synthetic Seawater (SSW) ionic medium simulating the major composition of natural seawater, at different salinities (5 less than or equal to S less than or equal to 45), and at t = 25 degreesC. Interactions with anionic components of SSW, considered as single sea salt, are determined by means of a complex formation model. By potentiometric measurements (ISE-H(+) and ISE-F(-) electrodes), the model has been extended to also consider interactions of organotins with carbonate and fluoride ions, which are other important components of seawater. Literature and new values of hydrolysis constants in …

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Polyacrylate Protonation in Various Aqueous Ionic Media at Different Temperatures and Ionic Strengths

The protonation constants of the polyacrylate anion (molecular mass 2000 Da) in Et4NI, Me4NCl, LiCl, LiNO3, NaCl, NaNO3, and KCl aqueous solution, were determined in a wide range of ionic strengths. A three-parameter approximation was used to express protonation constants as a function of the dissociation degree α, and their dependence on ionic strength was considered using a simple polynomial expansion. Differences in log KH between different data in different media were interpreted in terms of weak complex formation between polyacrylate and alkali metal cations. Measurements were also performed at different temperatures (15 ≤ T/°C ≤ 55) in order to calculate enthalpy and entropy changes f…

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Modelling of proton and metal exchange in the alginate biopolymer.

Acid-base behaviour of a commercial sodium alginate extracted from brown seaweed (Macrocystis pyrifera) has been investigated at different ionic strengths (0.1or=I/mol l(-1)or=1.0) and in different supporting electrolytes (Et4NI, NaCl, KCl, LiCl, NaCl+MgCl2), with the aim of examining the influence of ionic medium on the proton-binding capacity and of quantifying the strength of interaction with light metal ions in the perspective of speciation studies in natural aqueous systems. Potentiometric ([H+]-glass electrode) and titration calorimetric data were expressed as a function of the dissociation degree (alpha) using different models (Henderson-Hasselbalch modified, Högfeldt three parameter…

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Mercury(II) removal from aqueous solution by sorption onto alginate, pectate and polygalacturonate calcium gel beads. A kinetic and speciation based equilibrium study

Abstract Gel beads of calcium alginate, pectate and polygalacturonate salts have been tested as sorbent materials for mercury(II) removal from aqueous solutions. Physico-chemical properties of gel beads, defined by SEM–EDX, TGA and texture and density analysis, were correlated with gel beads sorption capacity towards Hg 2+ ion. A speciation study in aqueous solution was carried out to define the strength of interaction of mercury ion with the polymers investigated and to assess the more suitable experimental conditions to achieve the best effectiveness of Hg 2+ sorption by gel beads. On the basis of the speciation study, pH values in the 3–5.5 pH range were considered appropriated for mercu…

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Quantitative parameters for the sequestering capacity of polyacrilates towards alkaline earth metal ions

The complex formation constants of polyacrylic (PAA) ligands (1.4</=logN</=2.4, N=number of monomer units) with calcium and magnesium ions were determined in different ionic media at different ionic strengths, 0</=I</=1 mol l(-1), at t=25 degrees C. Experimental pH-metric data in the presence of Ca(2+) or Mg(2+) were firstly analysed in terms of apparent protonation constants, logK(H*), using the "three parameter model" proposed by Hogfeldt; differences in logK(H*), determined in different ionic media, were interpreted in terms of complex species formation. The only species present in the system M-PAA (M=Ca(2+) or Mg(2+)) is ML(2): attempts to find species of different stoichiometry were un…

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Adducts of organolead(IV) and organothallium(III) chlorides with N,N′-ethylenebis(salicylideneiminato)nickel(II) and bis(β-mercaptoethylamine)nickel(II)

Abstract Novel 1/1 adducts of organolead(IV) and organothallium(III) chlorides with the complexes N,N′-ethylenebis(salicylideneiminato)nickel(II) and bis(β-mercaptoethylamine)nickel(II) have been synthesized. Their configurations have been investigated in the solid state by IR and electronic spectroscopy and by magnetic measurements.

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POLYCYCLIC AROMATIC HYDROCARBONS IN MUD OF VULCANO ISLAND

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Sequestration of organomettalic compounds by synthetic and naturally occuring polycarboxylate ligands. Binding of monomethylmercury(II) by polyacrylic and alginic acids.

The sequestering capacity of synthetic and naturally occurring polycarboxylate ligands towards mono- methylmercury(II) was evaluated by stability quantitative data on the interaction of CH3Hgþ with different molecular weight synthetic polyacrylates (2 and 20 kDa average M.wt) and alginate (70– 100 kDa) extracted from brown algae Macrocystis pyrifera. The influence of ionic medium was evaluated by measurements on the CH3Hgþ-polyacrylate systems in NaNO3 medium at different ionic strengths (0.10, 0.25, 0.50 and 0.75mol Lÿ1), and a Debye–Hu¨ ckel type equation was used for the dependence of complex formation constants on ionic strength. Measurements on the CH3Hgþ - alginate system were carried…

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Studio delle proprietà acido-base del chitosano in soluzioni acquose di NaCl e interazioni con leganti carbossilici, a 25°C.

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The PAH composition in limpets (Patella vulgate L.) from the coasts of Sicily (Italy)

This article examines the presence, distribution, nature and sources of 19 Polycyclic Aromatic Hydrocarbons (PAH), in Patellae (patella vulgate L.) and seaweed (vulva) sampled in different stations of Sicilian coastal environments and analyzed for their polycyclic aromatic hydrocarbon (PAH) content. Analysis was performed by gas chromatography/mass spectrometry (GC/MS) with selected ion monitoring (SIM), after saponification of the sample and clean up of the extract. In the limpets the total concentration of polycyclic aromatic hydrocarbons ranged from 34 to 750 μg/Kg of dry matrix. The relative standard deviation (RSD) of the replicas on the concentrations of individual compounds ranged fr…

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Protonation Constants of Halloysite Clay Nanotubes

Halloysite is one of the most interesting nano-structured clay materials. It is similar to kaolin but has a hollow tubular structure that can be attributable to particular crystallization conditions. Typically, halloysite nanotubes (HNTs) are formed by 15 – 20 aluminosilicate layers, has a length of 1 ± 0.5 μm and inner and outer diameters of 1 - 30 and 30 - 50 nm, respectively [1,2]. In each layer the SiOH and the AlOH groups are disposed on the external and the internal surfaces, respectively. The particular structure of HNTs makes this kind of material very useful for different purposes in several fields. Among the various applications, worth of mention are: i) their use as additive for …

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Modelling of natural and synthetic polyelectrolyte interactions in natural waters.

In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et4NI and NaCl (for fulvic acid 0.1 < I /mol L− 1 < 0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5 < S < 45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na+, K+, Mg2+…

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Speciation of polyelectrolytes in natural fluids Protonation and interaction of polymethacrylates with major components of seawater.

Acid–base properties of two sodium polymethacrylates (W= 4000 and 5400 Da) were studied potentiometrically in aqueous solution at 25 °C. Measurements were made in different salt solutions: LiCl 0.1–1.5, NaCl 0.1–2, KCl 0.1–2, Et4NI 0.1–0.75 mol l − 1 , and in artificial seawater in the salinity range 10 S 45. Protonation data were analysed by two different models and the dependence of the relative parameters on ionic strength were calculated. Measurements performed in interacting media (alkali metal chlorides and artificial seawater) were interpreted in terms of complex formation, and the relative formation parameters are reported. Previous data on the interaction of a higher molecular weig…

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Speciation of dimethyltin(IV) – and trimethyltin(IV) – carbocysteinate and – glutamate systems in aqueous media

The formation of complex species in the dimethyltin(IV) and trimethyltin(IV)-carboxymethyl-L-cysteinate (carbocysteinate) systems in NaClaq, at different ionic strengths, and in a multicomponent Na+, K+, Ca2+, Mg2+, Cl- and SO42- medium representative of the seawater major composition, is discussed. Experimental results give evidence for the formation of the following species (L¼carbocysteinate): [(CH3)2Sn(L)]0, [(CH3)2Sn(HL)]+, [(CH3)2Sn(OH)(L)]-, [(CH3)2Sn(OH)2(L)]2- in the DMT–CCYS system, and [(CH3)3Sn(HL)]0, [(CH3)3Sn(L)]- and [(CH3)3Sn(OH)(L)]2- in the TMT-CCYS system. The ionic strength dependence of formation constants was taken into account by an extended Debye Huckel type equation…

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Effetti modulanti del poliacrilato sulla tossicità del TMT-CI in immunociti di Paracentrotus lividus.

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Sequestration of Organometallic Compounds by Poly –Acrylic Ligands

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Sequestration of alkyltin(IV) cations by complexation with amino-polycarboxylic chelating agents

Abstract The binding capacity of four amino-polycarboxylic ligands (APCs) [nitrilotriacetate (NTA), ethylenediamine- N , N , N′ , N′ -tetraacetate (EDTA), (S,S)-ethylenediamine- N , N ′-disuccinic acid (S,S-EDDS) and diethylenetriamine- N , N , N′ , N″ , N″ -pentaacetate (DTPA)] towards mono-, di- and tri-alkyltin(IV) cations [(CH 3 )Sn 3 + , (CH 3 ) 2 Sn 2 + , (C 2 H 5 ) 2 Sn 2 + , (CH 3 ) 3 Sn + or (C 2 H 5 ) 3 Sn + ] was studied, in aqueous solutions, by ISE-H + potentiometry, at I  = 0.1 mol L − 1 (NaCl) and at T  = 298.15 K. In all the systems R x Sn (4 − x)+  − APC (R = CH 3 or C 2 H 5 ) a strong 1:1 species is formed together with protonated, hydroxo and dinuclear complexes. The valu…

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Acid−Base Properties of Synthetic and Natural Polyelectrolytes: Experimental Results and Models for the Dependence on Different Aqueous Media

Protonation constants of several natural and synthetic humates and fulvates were determined by ISE-H+ potentiometry in different ionic media (alkali metal halides and tetraethylammonium iodide) at different ionic strengths and T ) 298.15 K. Experimental data obtained in previous studies of different synthetic (polyacrylates, polymethacrylates, polyacrylate-co-maleate) and naturally occurring (alginate, humic substances) polycarboxylates were also taken into account in the general analysis of acid-base properties of polyelectrolytes. Protonation constants were expressed as a function of the dissociation degree (R) using three models, namely, a simple linear model, the Ho¨gfeldt three-paramet…

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Sand clams of Ganzirri marine coastal lagoon in Messina (Italy). Extraction and ICP-MS analysis

This paper studies the possible forms or phases of heavy metals in sediments of a marine coastal lagoon, called Ganzirri, located in the Sicilian coast of the Messina’s strait by using sequential extraction. To reduce the extraction time of the Tessier method, the last step of speciation was carried out by mineralization in a microwave oven. Here we report the results of the distribution of As, Be, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, Se, Tl, V and Zn, in four fractions of sediments samples and the concentration of the same metals in clams. This study looked at three bivalve mollusc species, Tapes decussates, Chamelea gallina and Cardium edule, raised in the sediment considered and discussed the…

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Complex species formation in chitosan-phosphate and chitosan-nucleotide systems in NaCl aqueous solution.

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Variazione dei livelli di concentrazione di IPA in Patella coerulea nelle acque costiere siciliane

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LEAVES OFNERIUM OLEANDERL. AS BIOACCUMULATORS OF POLYCYCLIC AROMATIC HYDROCARBONS (PAH) IN THE AIR OF PALERMO (ITALY): EXTRACTION AND GC-MS ANALYSIS, DISTRIBUTION AND SOURCES

Polycyclic Aromatic Hydrocarbons (PAH) were determined in the leaves of Nerium oleander L. an evergreen plant that occurs widely in both urban and rural areas, to monitor the degree of pollution in the urban area of Palermo (Italy) compared to remote areas. Twenty sites (urban roadside, urban, urban park, suburban and rural) in and around Palermo city were investigated. The purpose of this research was to investigate concentration levels and distribution patterns and relate them to possible sources. Analysis of 19 PAH was performed by gas chromatography/mass spectrometry (GCMS) using selected ion monitoring (SIM). The total amount of PAH ranged from 10 to 166 μg/Kg d.w. Each source gives ri…

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Protonation constants and association of polycarboxylic ligands with the major components of seawater

Apparent protonation constants, log βjH*, of 11 carboxylic acids were determined potentiometrically ([H+]-glass electrode) in artificial seawater containing six of the major components (Na+, K+, Mg2+, Ca2+, Cl-, and SO42-) at different salinities:  S (‰) = 5, 15, 25, 35, 45. Values of log βjH* were fitted by the simple polynomial equation log βjH* = log TβjH + a1S1/2 + a2S + a3S3/2 (log TβjH = protonation constants at infinite dilution; a1, a2, a3 = empirical parameters), for mono-, di-, and tricarboxylates. For carboxylic anions with charge < −3, a better fit was obtained using the equation log βjH* = log TβjH + b1I + b0z* log(1 + b2I) (b0, b1, b2 = empirical parameters, z* = square sum of…

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Hydrolysis and chemical speciation of dioxouranium(VI) ion in aqueous media simulating the major ion composition of seawater

Abstract The hydrolysis and chemical speciation of the dioxouranium(VI) ion at 25 °C was studied in a number of binary electrolytes (LiCl, NaCl, MgCl2, CaCl2, Na2SO4) and some mixtures (NaCl–Na2SO4, NaNO3–Na2SO4, CaCl2–MgCl2) as well as artificial seawater (SSWE) as a function of ionic strength. The results in LiCl, CaCl2 and MgCl2 solutions confirmed the formation of (UO2)2(OH)22+, (UO2)3(OH)42+, (UO2)3(OH)5+ and (UO2)3(OH)7− species (at I=0 mol l−1: log Tβ22=−5.76, log Tβ34=−11.82, log Tβ35=−15.89 and log Tβ37=−29.26). For NaNO3, NaCl and artificial seawater the hydrolysis constant for the formation of the UO2(OH)+ species was also determined (at I=0 mol l−1: log Tβ11=−5.19). The results …

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Thermodynamics of Proton Binding of Halloysite Nanotubes

In this paper, new information on physical and chemical properties of the widely used nanostructured Halloysite mineral are reported. Given that the Halloysite has a tubular structure formed by a variable number of wrapped layers containing Si-OH and Al-OH groups, their proton binding affinity was measured at different ionic strengths and ionic media by means of potentiometric measurements in heterogeneous phase. One protonation constant for the Si-OH groups and two for the Al-OH groups were determined. The protonation constant values increase with increasing of the ionic strength in all the ionic media. This suggests that the presence of a background electrolyte stabilizes the protonated s…

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Complessi di derivati di organostagno(IV) con S-carbossi-L-cisteina e acido glutammico in NaCl a diverse forze ioniche

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Tin(IV) complexes with O-ethyl(N-ethyl-N,N-dimethylammoniomethyl)phosphonate

Abstract O,O-Diethyl-(N,N-dimethylaminomethyl)phosphonate undergoes ethyl migration leading to O-ethyl-(N-ethyl-N,N-dimethylammoniomethyl)phosphonate (L). Several new complexes of tin(IV) and organotin(IV) chlorides with the title ligand have been synthesized. The stoichiometry of the obtained complexes is as follows: (R3SnCl)2 · L (R=Me, Bu, Ph), R2SnCl2 · L (R=Me, Bu, Ph), RSnCl3 L (R=Me, Ph) and SnCl4 · L. All the complexes have been studied in solution by means of 1H-, 13C-, 31P- and 119Sn-NMR spectroscopy. Their solid state structures have been investigated by means of Mossbauer spectroscopy and the molecular structure of the complex (Ph3SnCl)2 · L has been determined by X-ray crystall…

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Studio della capacità sequestrante della biomassa nei confronti dello ione rame (II)

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Protonation constants of carbonate in aqueous tetra-alkyl ammonium salts at 25 °C

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Complex formation of copper(II) and cadmium(II) with pectin and polygalacturonic acid in aqueous solution. An ISE-H + and ISE-Me 2+ electrochemical study

The acid-base properties of pectin and its ability to complex with copper(II) or cadmium(II) were quantitatively determined in order to define the ability of this natural polyelectrolyte to sequester metal ions. Potentiometric measurements carried out at different ionic strengths (0.1 - 0.7 mol L-1, in Na+ ionic medium) allowed us to define the acid-base properties of pectin together with the dependence of the protonation constants on ionic strength and to calculate the protonation constant at infinite dilution. The formation of complex species between pectin and copper(II) or cadmium(II) was investigated potentiometrically (using H+, Cu2+ and Cd2+ Ion Selective Electrodes, ISEs) in NaNO3 a…

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Capacità sequestrante di leganti S-donatori nei confronti di CH3Hg+

L’interesse nei confronti della chimica di coordinazione del mercurio(II) deriva dalla sua tossicità intrinseca. Sebbene tutte le forme di mercurio siano tossiche, gli effetti sull’ambiente e sull’uomo sono in genere legati alle trasformazioni ambientali di Hg inorganico a metilmercurio. L’elevata tossicità del metilmercurio(II) per gli esseri umani deriva dall’affinità del mercurio(II) nei confronti di residui cisteinil solfuri. I tioli a basso peso molecolare costituiscono i vettori per il trasporto e la distribuzione di mercurio nell’organismo umano a causa del fenomeno del "mimetismo molecolare”. Uno studio della chimica in soluzione del metilmercurio(II) in presenza di tali leganti for…

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Aqueous solution chemistry of alkyltin(IV) compounds for speciation studies in biological fluids and natural waters

Abstract Organotin(IV) cations behave as Lewis acids of different strength depending on the charge, according to the following acidity scale: RSn3+ > R2Sn2+ > R3Sn+. For this reason they can react with Lewis bases containing –O, –N, –S donor groups to form complex species of different stability. Complex formation of organotin(IV) moieties with a great number of inorganic and organic ligands in aqueous solution is reviewed here in the light of their environmental and biological impact. To this end, complex species formation was considered in different ionic media and at different ionic strengths, with reference to the composition of natural waters and biological fluids. In particular, the in…

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Interactions of Dioxouranium(VI) with Amines in Aqueous Solution

The interaction of the dioxouranium(VI) ion with five low molecular weight polyamines (ethylenediamine, putrescine, cadaverine, spermidine, and spermine) and with poly(allyl)amine (15 kDa) was studied potentiometrically (ISE-H + glass electrode) at T ) 298.15 K. Investigations were carried out in NaNO3 ionic medium, at I ) 0.1 mol · L -1 (and 0.5 mol · L -1 for poly(allyl)amine only), in the pH range 3.5 to 5.5, before the formation of uranyl insoluble species. The results gave evidence for the formation of two species, namely, UO2L 2+ and UO2L(OH) + for the diamine systems (ethylenediamine, putrescine, cadaverine), UO2L 2+ and UO2LH 3+ for spermidine, and UO2LH 3+ and UO2LH2 4+ for spermin…

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Use of amino–polycarboxylic chelating agents for the sequestration of (CH3)Hg+ ion in aqueous solution

Among the mercury organic derivatives, mono-methylmercury (MMHg) is by far the most toxic form of mercury because of its high capacity to enter biological membranes and accumulate in living organisms [1], as shown by the biomagnification factors: ~104 from water to edible shell-fish (mussels), and 106 –108 from water to big fishes (e.g. tuna fish) at the top of food chain [2]. The presence of complexing agents in the environment, which form soluble complex species with MMHg, favours the mobility of the ion in the aquatic ecosystems. Among anthropogenic complexing molecules, the most used ones are the aminopolycarboxylic chelating agents (usually called with the acronym APC) which are employ…

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Sorption of Pd(II) ion by calcium alginate gel beads at different chloride concentrations and pH. A kinetic and equilibrium study

Abstract A kinetic and thermodynamic study on the sorption ability of calcium alginate gel beads towards Pd(II) ion was made in aqueous solution at different pH and chloride concentrations. The experimental conditions adopted in the sorption experiments were established on the basis of a speciation study on the Pd 2+ -AA system in which all the side reactions, such as the hydrolysis of Pd(II), the protonation of alginate and the interactions of the ligand and the metal ion with ions of ionic medium were taken into account. In the pH range 2–5 and at chloride concentration in the range 0 ⩽ C Cl - /mmol L −1  ⩽ 10 the gel beads showed good sorption ability towards Pd(II) ion as confirmed by k…

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Absorption of polycyclic aromatic hydrocarbons by pinus bark: analytical method and use for environmental pollution monitoring in the Palermo area (Sicily, Italy)

Abstract In the light of using biomaterial as pollutants sorbents for the environmental biomonitoring, we report here the results of the absorption of polycyclic aromatic hydrocarbons (PAHs) by pine bark. Quantitative analysis of 19 different polycyclic aromatic compounds was performed, after Soxhlet extraction in dichloromethane, by means GC–MS technique. Pinus was chosen due to its wide distribution in the Mediterranean area. The passive absorption of PAH by pine bark in the metropolitan areas allowed us to evaluate the air quality of Palermo. The obtained results showed a very high range of PAHs concentrations, from 33 μg/kg (bark dry weight), as ΣPAHs, at the control site to 1015 μg/kg …

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Studio della sequestrazione dello ione cadmio da parte di leganti s-donatori

La presenza in natura del cadmio è dovuta principalmente al suo uso in svariati settori dell’industria [1] ed in misura minore al suo rilascio durante i processi di demineralizzazione delle rocce. La elevata tossicità dello ione cadmio [2] nei confronti degli esseri viventi, animali e vegetali, è dovuta alla elevata affinità che questo catione mostra nei confronti della maggior parte dei gruppi leganti presenti nelle molecole biologicamente attive. In particolare i leganti tiolici presenti nei residui amminoacidici, soprattutto quelli a basso peso molecolare rappresentano i vettori principali attraverso il quale avvengono i fenomeni di trasporto e di distribuzione del cadmio nell’organismo …

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Identification of Polycyclic Aromatic Hydrocarbons (PAHs) in the black crusts of Sicilian stone monuments: distribution and sources

Polycyclic Aromatic Hydrocarbons are a family of compounds with known carcinogenic potential; their properties of lipophilicity, low water solubility and adsorption to particles and sediments make them a potentially dangerous group of chemicals and a threat to the environment and its bio-resources. The concentrations of total Polycyclic Aromatic Hydrocarbons (PAHs) and 19 individual compounds in 8 black crusts sampled from historical building of Palermo (Italy) were analyzed, by gas chromatography/mass spectrometry (GC/MS) in selected ion monitoring (SIM) mode. PAH concentrations ranged from 78 to 9798 g/Kg of dry matrix. The resulting distributions and molecular ratios of specific compo…

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Binding of acrylic and sulphonic polyanions by open-chain polyammonium cations

Abstract The interactions between some acrylic and sulphonic polyanions and some protonated amines (diamines NH 2 -(CH 2 ) x -NH 2 , x =2,…,10; linear tri-, tetra-, penta- and hexa-amines) were studied potentiometrically in aqueous solution, at 25°C. For both types of polyanions AL 2 H i (L − , monomer of polyanion, A, amine) species are formed, with i =1,…, n ( n =number of amino groups in the amine). The stability of these species is strictly dependent on the polyammonium cation charge, and fairly independent of the type of amine (in diamine species maximum stability is observed for x =4, 5). Acrylic and sulphonic polyanion complexes are considerably stronger than analogous species formed…

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Metal distribution in organic and inorganic fractions of soils from Sicily

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Hydrolysis and chemical speciation of (C2H5)2Sn2+, (C2H5)3Sn+ and (C3H7)3Sn+ in aqueous media simulating the major composition of natural waters

The hydrolysis of (C 2 H 5 ) 2 Sn 2+ , (C 2 H 5 ) 3 Sn + and (n-C 3 H 7 ) 3 Sn + has been studied, by potentiometric measurements ([H + ]-glass electrode), in NaNO 3 , NaCl, NaCl/Na 2 SO 4 mixtures and in a synthetic seawater (SSWE), as an ionic medium simulating the major composition of natural seawater, at different ionic strengths (0 ≤ I ≤ 5 mol dm -3 ) and salinities (15 ≤ S ≤ 45), and at t = 25 °C. Five hydrolytic species for (C 2 H 5 ) 2 Sn 2+ , three for (C 2 H 5 ) 3 Sn + and two for (C 3 H 7 ) 3 Sn + are found. Interactions with the anion components of SSWE, considered as single-salt seawater, are determined by means of a complex formation model. A predictive equation for the calcul…

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Interaction of Alkyltin(IV) Compounds with Ligands of Interest in the Speciation of Natural fluids: Complexes of (CH3)2Sn2+ with Carboxylates

Complex formation by (CH3)2Sn 2+ with acetate (ac), malonate (mal), 1,2,3-propanetricarboxylate (tricarballylate, tca) and 1,2,3,4-butanetetracarboxylate (btc) ligands in aqueous solution is reported. The study has been performed by potentiometry ([H + ]‐glass electrode) at T = 25 °C, and in the 0 < I < 1 mol dm 2 3 ionic strength range. In order to evaluate the salt effects on the formation constants of the complex species, and to contribute to the definition of the chemical speciation of diorganotin(IV) compounds in natural waters where carboxylic ligands are naturally present, interactions of NaCl (which is the major component of all natural fluids), with the components of the systems un…

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Interazione di UO22+, Cd2+, Zn2+, Cu2+ con acido poliacrilico ed acidi fulvici

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Modelling of natural synthetic polyelectrolyte interactions in natural waters by using SIT, Pitzer and Ion Pairing approaches

Abstract In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et 4 NI and NaCl (for fulvic acid 0.1  − 1 S single salt ” BA, with cation B and anion A representing all the major cations (Na + , K + , Mg 2+ , Ca 2+ ) and anions (Cl − , SO 4 2− ) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous sp…

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The importance of chemical speciation studies in the characterization of natural waters

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Sequestration of (CH3)Hg+ by amino‐polycarboxylic chelating agents

Abstract The speciation of mono-methylmercury(II) cation (MeHg+) in the presence of Nitrilotriacetate (NTA), Ethylenediamine-N,N,N′,N′-tetraacetate (EDTA), diethylenetriamine-N,N,N′,N″,N″-pentaacetate (DTPA) and (S,S)- Ethylenediamine-N,N′-disuccinic acid (S,S-EDDS) was investigated at I = 0.1 mol L− 1 (NaCl) with the aim to assess a trend of sequestering capacity of the amino‐polycarboxylic (APCs) ligand class towards this cation in aqueous solution. The results obtained gave evidence for the formation of a mononuclear [MeHg(APC)] complex species, differently protonated MeHg(HiL) species (i = 1 to 3, depending on the APC considered), a mixed hydroxo species [MeHg(APC)(OH)] and a binuclear …

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Speciation of Cadmium - D-penicilamine, mercaptosuccinic acid and glutathione systems in NaNO3 ionic medium

Cadmium shows a high affinity towards most of the binding groups present in biologically active molecules. In particular, the thiol ligands present in the amino acid residues, are the main vectors through which transport and distribution of cadmium in the human body occur. In spite of the large number of investigations reported in the literature about the toxic effects of cadmium and its environmental impact, relatively few quantitative data are reported on the stability of species formed by the interaction between Cd2+ and S-donor ligands in aqueous solution. Therefore, it is difficult to define the speciation picture of this element in natural waters and biological fluids where thiol liga…

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Sequestration of biogenic amines by alginic and fulvic acids.

The interaction of natural (alginic and fulvic acids) and synthetic (polyacrylic acid 2.0 kDa) polyelectrolytes with some protonated polyamines [diamines: ethylendiamine, 1,4-diaminobutane (or putrescine), 1,5-diaminopentane (or cadaverine); triamines: N-(3-aminopropyl)-1,4diaminobutane (or spermidine), diethylenetriamine; tetramine: N.N'-bis(3-aminopropyl)-1,4-diaminobutane (or spermine); pentamine: tetraethylene-pentamine; hexamine: pentaethylenehexamine] was studied at T=25 degrees C by potentiometry and calorimetry. Measurements were performed without supporting electrolyte, in order to avoid interference, and results were reported at I=0 mol L(-1). For all the systems, the formation of…

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Solubilità, proprietà acido - base e coefficienti di attività del chitosano in soluzione acquosa a 298.15°K

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A study on the acid-base properties of pectin and poly-galacturonic acid

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Idrocarburi policiclici aromatici nelle croste nere presenti in edifici di zone fortemente antropizzate: aspetti analitici e sanitari

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Speciation of organotin compounds in NaCl aqueous solution: interaction of mono-, di- and tri-organotin(IV) cations with nucleotide 5′ monophosphates

Formation constants for complex species of mono-, di- and tri-alkyltin(IV) cations with some nucleotide 5'-monophosphates (AMP, UMP, IMP and GMP) are reported, at T=25°C and at I = 0.16 mol 1 -1 (NaCI). The investigation was performed in the light of speciation of organometallic compounds in natural fluids in the presence of nucleotides whose biological importance is well recognized. The simple and mixed hydrolytic complex species formed in all the systems investigated in the pH range 3-9 are (L = nucleotide; M = organotin cation R x Sn (4-x)+ , with x = 1 to 3): ML + , ML(OH)° and ML(OH) 2 - for the system CH 3 Sn 3+ -L (L = AMP, IMP, UMP); ML 0 and ML(OH)-for the system (C 2 H 5 ) 2 Sn 2+…

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Polyacrylates in aqueous solution. The dependence of protonation on molecular weight, ionic medium and ionic strength

Abstract The protonation constants of polyacrylates with different molecular weights ( W =2000–750 000 Da) were determined in different ionic media (alkali metal chlorides and nitrates, tetraalkylammonium chlorides), at 25 °C, by potentiometric measurements (H + –glass electrode). Literature data were also considered. Different models used to analyse protonation data were compared: the first was the modified Henderson–Hasselbalch two-parameter equation, and the second was the three-parameter equation proposed by Hogfeldt. The dependence on the ionic strength of the different supporting electrolytes and all the protonation parameters involved in the two models showed the trend Et 4 N + ≫Li +…

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Uranium(VI) sequestration by polyacrylic and fulvic acids in aqueous solution

Stability data on the formation of dioxouranium(VI) species with polyacrylic (PAA) and fulvic acids (FA) are reported with the aim to define quantitatively the sequestering capacity of these high molecular weight synthetic and naturally occurring ligands toward uranium(VI), in aqueous solution. Investigations were carried out at t = 25 °C in NaCl medium at different ionic strengths and in absence of supporting electrolyte for uranyl–fulvate (\( {{\text{UO}}_{2}}^{2+} \)–FA) and uranyl–polyacrylate (\( {{\text{UO}}_{ 2}}^{ 2+ } \)–PAA, PAA MW 2 kDa) systems, respectively. The experimental data are consistent with the following speciation models for the two systems investigated: (i) UO2(FA1),…

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Alginate gel beads filled with halloysite nanotubes

Abstract Novel hybrid gel beads with a well defined and controlled size formed by alginate biopolymer and halloysite (Hal) nanotubes were designed, prepared and characterized from the physico-chemical viewpoint. The thermogravimetry made it possible to determine the water content, the total as well as the local compositions of Hal into the gel beads. Dielectric spectroscopy evidenced that Hal reduced the fluctuation of ions. The SEM micrographs showed that the dried beads exhibit a rough surface, with pores in the micrometer range. In addition, the concentration of nanotubes was higher into the bead core at a higher overall loading. The performance of these materials was verified with the s…

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PAHs and Humic acids

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Effect of seawater salt on the protonation of some classes of ligands

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Hydrolysis of Monomethyl-, Dimethyl-, and Trimethyltin(IV) Cations in Fairly Concentrated Aqueous Solutions at I = 1 mol L-1 (NaNO3) and T = 298.15 K. Evidence for the Predominance of Polynuclear Species

The hydrolysis of methyltin(IV) cations at fairly high concentrations was investigated to evaluate the formation of polynuclear species in aqueous solution. The hydrolysis of monomethyltin(IV), dimethyltin(IV), and trimethyltin(IV) was studied by potentiometry at T = 298.15 K and at I = 1 mol L-1 in NaNO3 aqueous solutions. The results obtained gave evidence for the formation of the following polynuclear species, in addition to the mononuclear species already reported, which were also considered in the models proposed for the three systems investigated: [(CH3)Sn(OH)3]0, [(CH3)Sn(OH)4]-, [((CH3)Sn)2(OH)4]2+, [((CH3)Sn)2(OH)5]+, [((CH3)Sn)2(OH)7]-, [((CH3)Sn)3(OH)5]4+, [((CH3)Sn)3(OH)7]2þ, [(…

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The role of sediments in the detection of the quality of sea water and its potential environmental implications, the case of Mondello bay (Palermo, Italy)

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Acid-base properties of halloysite clay nanotubes in NaCl medium

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Interaction of methyltin(IV) compounds with carboxylate ligands. Part 1: formation and stability of methyltin(IV)–carboxylate complexes and their relevance in speciation studies of natural waters.

Quantitative data on the stability of mono-, di- and trimethyltin(IV)-carboxylate complexes (acetate, malonate, succinate, malate, oxydiacetate, diethylenetrioxydiacetate, tricarballylate, citrate, butanetetracarboxylate and mellitate) are reported at t=25°C and I → 0 mol l - 1 . Several mononuclear, mixed proton, mixed hydroxo and polynuclear species are formed in these systems. As expected, the stability trend is mono- > di- > trimethyltin(IV) and mono < di < tri < tetra < hexa for the organotin moieties and carboxylate ligands investigated, respectively. Moreover, ligands containing, in addition to carboxylic,-O-and-OH groups show a significantly higher stability with respect to analogou…

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Speciation of chitosan with low and high molecular weight carboxylates in aqueous solution

Quantitative data on the speciation of chitosan (310 kDa) with low and high molecular weight carboxylates in aqueous solution are reported. The following carboxylic ligands were considered: monocarboxylate (butyrate); dicarboxylates (malonate, succinate, azelate); tricarboxylate (1,2,3-propa- netricarboxylate); tetracarboxylate (1,2,3,4-butanetetracarboxylate); polyacrylates (2.0 and 20 kDa); polymethacrylate (5.4 kDa). The investigation was performed by potentiometry at t 1/4 25 C, at low ionic strength (without addition of supporting electrolyte) and at I 1/4 0:15 mol L 1 (NaCl). For all the systems the formation of (chitosan)LHi species was found (L 1/4 carboxylic ligand; i 1/4 1 to 4 de…

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In vitro effects of methylmercury on ascidian (Styela plicata) immunocyte responses

This study shows that high methylmercury concentrations are cytotoxic for Styela plicata hemocytes, whereas sublethal concentrations affect immunocyte responses. Moreover, hemocytes exposed to the xenobiotic present a significantly enhanced phenoloxidase activity as revealed in the hemocyte lysate supernatant compared with the control. Although the cytotoxic activity of S. plicata hemocytes toward rabbit erythrocytes is a PO-dependent cell-target reaction due to quinone products, it was significantly decreased by suitable methylmercury concentrations in the medium. The same xenobiotic concentrations decreased the hemocyte phagocytic activity toward yeast. In both the responses cell-target c…

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EFFECT OF IONIC STRENGTH AND MEDIUM COMPOSITION ON THE REMOVAL OF Pb2+ BY ALGINATE GEL BEADS. DPVASV AND ICP-OES MEASUREMENTS.

The biosorption, i.e. a passive sequestering process by metabolically inactive biomass, shows a growing interest for toxic metal ions removal from contaminated aqueous solutions (1), such as municipal and industrial wastewaters. Since the sorption mechanism occurs mainly by ion exchange between the metal ion present in solution and the counter ion of the biopolymer (2), the efficiency of the sorption process largely depends on ionic strength and on the medium composition of solution containing the metal ion to be removed. In order to evaluate quantitatively the influence of ionic strength and medium on the metal removal process by the biomass, we report here results of a study on the sorpti…

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Speciation of Low Molecular Weight Carboxylic Ligands in Natural Fluids: Protonation Constants and Association with Major Components of Seawater of Oxydiacetic and Citric Acids

Abstract The interaction of oxydiacetate and citrate with the major components of seawater has been studied potentiometrically, at 25°C, in an artificial seawater (containing Na+, K+, Ca2+, Mg2+, Cl− and SO42−) at different salinities (5–45‰). Apparent protonation constants were calculated, from potentiometric data, and estimated, using an appropriate complex formation model. Formation constants of complexes formed by oxydiacetate and citrate and the cation of seawater (the inorganic content of seawater being considered as a single 1 : 1 salt) were determined. The single salt approximation for the major inorganic components of seawater, which is a good tool in estimating the mean strength o…

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Interaction of methyltin(IV) compounds with carboxylate ligands. Part 2: Formation thermodynamic parameters, predictive relationships and sequestering ability.

Thermodynamic data of mono-, di- and tri-methyltin(IV)-carboxylate complexes (acetate, malonate, succinate, oxydiacetate, diethylenetrioxydiacetate, malate, citrate, 1,2,3-tricarballylate, 1,2,3,4-butanetetracarboxylate, 1,2,3,4,5,6-benzenehexacarboxylate) in aqueous solution are reported at t = 25 °C and I = 0 mol l−1. Thermodynamic parameters obtained were analysed to formulate empirical predictive relationships as a function of different parameters, such as the number of carboxylate groups of the ligand and the charge of the alkyltin(IV) cation. Sequestration diagrams of citrate and 1,2,3-tricarballylate towards alkyltin(IV) cations at different pH values are also reported and discussed.…

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Adsorption of polyciclic aromatic hydrocarbons (PAHs) by pine barks and their use for environmental pollution monitoring in the Palermo (ITALY) area

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Modelling of protonation constants of halloysite clay nanotubes in various aqueous media, at different ionic strengths

In the last decade nanoparticles have assumed more and more importance because of their particular properties mainly due to the nanometer-scale dimensions that confer them a large surface/volume ratio. Among nanomaterials one of the most studied is the halloysite that, as well as the other natural clay minerals is safe for human and environmental friendly. Halloysite is abundant and cheap and is present in large deposits worldwide like those in New Zealand, France, Belgium and China [1,2]. It is similar to kaolin but has a hollow tubular structure that can be attributable to particular crystallization conditions. Typically, halloysite nanotubes (HNTs) are formed by 15 – 20 aluminosilicate l…

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SORPTION OF CD2+ AND CU2+ IONS FROM AQUEOUS SOLUTIONS BY ALGINATE AND ALGINATE/PECTIN GEL BEADS.

Removal of toxic metal ions from natural waters, wastewaters and contaminated sites is of great importance for the health of living organism and for environmental protection (1). Alternatively to the conventional chemical treatments, such as precipitation, reverse osmosis, etc, that are expensive and of high environmental impact, the use of low cost and environmental friendly sorbent materials is a very promising new technology for meal ions removal (2,3). The most investigated sorbent materials are of organic origin derived from the natural biomass (algae, fungi, bacteria) and from industrial processes, such as wood, agriculture, fishery, textile manufacturing, etc. Also some inorganic mat…

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Interactions UO22+ - amines

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Complexes of chitosan with low and high molecular weight carboxylic ligands in aqueous solution.

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On the Complexation of Cu(II) and Cd(II) With Polycarboxyl Ligands. Potentiometric Studies With ISE-H+, ISE-Cu2+, and ISE-Cd2+

The interaction of Cu2+ and Cd2+ ions with polyacrylates (PAA, 2 kDa and 100 kDa), polymetacrylate(PMA, 5.4 kDa), and alginate (AA, 70 kDa to 100 kDa) was studied by potentiometry, using ISE-Cu2+, ISE-Cd2+, and ISE-H+ electrodes. The investigations were performed in NaNO3 aqueous solutions, in the ionic strength range 0.10 e I (mol ·L-1) e 0.75, at T ) 298.15 K. The “diprotic-like model” was used to explain the acid-base behavior of the polycarboxylates under investigation (for this model, the monomeric unit of the polyelectrolyte is considered as a dicarboxylate). The results give evidence for the formation of the ML species in all the systems investigated. In addition, the MLH species was…

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Experimental and robust modeling approach for lead(II) uptake by alginate gel beads: influence of the ionic strength and medium composition.

Abstract Systematic kinetic and equilibrium studies on the lead ions removal ability by Ca-alginate gel beads have been performed by varying several internal parameters, namely, number of gel beads, nature and composition of the ionic medium and pH, which allowed us to model a wastewater in order to closely reproduce the composition of a real sample. Moreover, the effects brought about the different ionic species present in the reacting medium have been evaluated. Differential Pulse Anodic Stripping Voltammetry (DP-ASV), has been systematically used to perform kinetic and equilibrium measurements over continuous time in a wide range of concentration. Kinetic and equilibrium data have been q…

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Modeling S-carboxymethyl-L-cysteine protonation and activity coefficients in sodium and tetramethylammonium chloride aqueous solutions by SIT and Pitzer equations

Solubility and acid–base properties of S-carboxymethyl-l-cysteine (carbocysteine, ccys) in NaClaq and tetramethylammonium chloride, (CH3)4NClaq ,a tt =2 5 ◦ C and at different ionic strengths were investigated. Solubility was studied at 1.0 ≤ I (mol L −1 ) ≤ 5.0 for NaClaq and 1.0 ≤ I (mol L −1 ) ≤ 3.0 for (CH3)4NClaq, while potentiometric measurements (by ISE-H + , glass electrode) were performed at 0.1 ≤ I (mol L −1 ) ≤ 5.0 for NaClaq and 0.5 ≤ I (mol L −1 ) ≤ 3.0 for (CH3)4NClaq. Solubility data allowed us to determine Setschenow constants and activity coefficients of neutral carbocysteine (H2ccys). Dependence on ionic strength and ionic medium of protonation constants and activity coeff…

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Speciation of low molecular weight ligands in natural fluids: protonation constants and association of open chain polyamines with the major components of seawater.

Abstract The interaction of five open chain polyamines (ethylenediamine (en), diethylenetriamine (dien), trietylenetetramine (trien), tetraethylenepentamine (tetren), spermine (sper)) with the major components of seawater was studied potentiometrically at 25°C, in an artificial seawater (containing Na+, K+, Mg2+, Ca2+, Cl− and SO42−) at different salinities (5–45‰). Potentiometric data were interpreted in terms of both the apparent protonation constants of polyamines and the formation constants of complexes formed by unprotonated or protonated amines and the cation and the anion of seawater (the inorganic content of seawater being considered as a single 1:1 salt). Some empirical relationshi…

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Speciation of Organic Matter in Natural Waters-interaction of polyacrylates and polymethacrylates with major cation components of seawater

Abstract The speciation of some high molecular weight polycarboxylates was studied in different ionic media. Polyacrylates here investigated ( W =2.0, 5.1 and 20.0 kDa) form weak species with alkali metal cations ( K =10 2 mol l −1 , t =25 °C, I =0 mol l −1 ) and quite stable complexes with alkaline earth metal cations ( K >10 6 mol l −1 , t =25 °C, I =0 mol l −1 ). Results are reported from experiments performed in a multicomponent electrolyte solution simulating the major composition of seawater (artificial seawater). Protonation constants in this medium are expressed as a polynomial function of S 1/2 ( S =salinity) and the sharp lowering with respect to values obtained in non-interacting…

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Kinetic and equilibrium study for cadmium and copper removal from aqueous solutions by sorption onto mixed alginate/pectin gel beads

Abstract Kinetic and equilibrium studies have been carried out to evaluate Cd(II) and Cu(II) sorption from aqueous solution by calcium alginate and new synthesized hybrid calcium alginate/pectate gel beads with different alginate/pectate concentration ratios. Physical and chemical properties of the beads were characterized by different techniques (SEM, EDX, TGA). The best experimental pH conditions were selected on the basis of a study on the acid–base properties of pectin and alginate in aqueous solution and their ability to act as sequestering agents for copper(II) and cadmium(II) ions. Calcium released during the sorption process was determined in order to elucidate a possible ion exchan…

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Occurrence and concentrations of PAHs in clams and sediments of marine coastal lagoons of Ganzirri (Italy). Extraction and GC-MS analysis distributions and sources

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Acid-base behaviour of fulvic acids in seawater at different salinities

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Mercury(II) removal from aqueous solutions by alginate and pectin sorbent materials. Kinetic and equilibrium study

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Polycyclic Aromatic Hydrocarbons in Sediments of Marine Coastal Lagoons in Messina, Italy: Extraction and GC/MS Analysis, Distribution and Sources

The content of 21 polycyclic aromatic hydrocarbons (PAHs) has been determined in 16 samples of sediments collected from Ganzirri and Faro marine coastal lagoons in Messina (Italy). Analysis was performed by gas chromatography/mass spectrometry (GC/MS) in selected ion monitoring (SIM) mode. The total concentration of polycyclic aromatic hydrocarbons (PAHs) ranged from 74 to 5755 ...g/Kg of dry matrix. The resulting distributions and molecular ratios of specific compounds have been discussed in terms of sampling location and origin of organic matter. The results obtained show that levels of contamination are not homogeneous throughout the stations, while the relative distributions of PAH are…

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Protonation of Carbonate in Aqueous Tetraalkylammonium Salts at 25°C.

Protonation constants of carbonate were determined in tetramethylammonium chloride (Me4NClaq 0.1≤I/mol kg−1 ≤4) and tetraethylammonium iodide (Et4NIaq 0.1≤I/mol kg−1 ≤1) by potentiometric ([H+]-glass electrode) measurements. Dependence of protonation constants on ionic strength was taken into account by modified specific ion interaction theory (SIT) and by Pitzer models. Literature data on the protonation of carbonate in NaClaq (0.1≤I/mol kg−1 ≤6) were also critically analysed. Both protonation constants of carbonate follow the trend Et4NI>Me4NCl > NaCl. An ion pair formation model designed to take into account the different protonation behaviours of carbonate in different supporting electr…

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Complex species formation in the pectin-cadmium(II) and pectin-copper(II) systems in aqueous solution.

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Pelargonium leaves as bioindicator of polynuclear aromatic hydrocarbons (PAHs): Analytical method and evaluation of sources and air quality in Palermo (ITALY) area

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Kinetic and equilibrium study for Pd(II) removal from aqueous solution by sorption onto calcium alginate gel beads

The more and more increasing use of catalytic converters to reduce the dangerous NOx and CO emission in the atmosphere by vehicle traffic produces a corresponding increase of palladium in the environment [1]. Among the so-called “platinum group Elements” (PGE), elemental palladium seems to be the most hazardous one because it can be easily and quickly oxidized to palladium(II) when put in contact with soil. The presence of palladium oxidized form is of great concern owing to its recognized toxicity towards plants, animals and humans. Therefore, as for the classical “heavy metals”, a removal of this element from the environment is needed and a subsequent recovery for its potential re-use is …

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The interaction of amino acids with the major constituents of natural waters at different ionic strengths

Abstract The interaction of amino acids with the major constituents of natural waters has been studied potentiometrically by determining protonation constants at different ionic strengths (e.g., I ≤5.6 mol (kg H 2 O) −1 (NaCl)) and in artificial seawater (containing Na + , K + , Ca 2+ , Mg 2+ , Cl − and SO 4 2− ) at different salinities. For glycine determinations in mixed NaCl–MgCl 2 , electrolyte solutions were also performed. The data included in this work, together with some already published, make it possible to calculate parameters for dependence on ionic strength using different models, i.e. an extended Debye–Huckel type equation and Pitzer equations. The results can be interpreted b…

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Weak alkali and alkaline earth metal complexes of low molecular weight ligands in aqueous solution

This work is aimed at reviewing the chemical literature dealing with thermodynamic aspects of the weak complex formation (species with log K values less than about 3) between alkali and alkaline earth metal ions with low molecular weight inorganic and organic ligands in aqueous solution. The following ligands (up to hexavalent anions) were examined in detail: (i) hydroxide, chloride, sulfate, carbonate and phosphate as inorganic, and (ii) carboxylates, amines, amino acids, complexones and nucleotides as organic ligands. The paper also identifies the main reasons responsible for the dispersion of the stability data on ion pairs in the literature. When possible, the trend of stability for the…

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INTERACTIONS OF DI- AND TRI-METHYLTIN(IV) WITH S-CARBOXYMETHYL-L-CYSTEINE AND GLUTAMIC ACID IN DIFFERENT AQUEOUS MEDIA AND AT DIFFERENT IONIC STRENGTHS

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Analytical method for metal distribution in the organic and inorganic fractions of sediment: a case-study on sedimento f Ganzirri marine coastal lagoon in Messina (Italy). Extraction and ICP-MS analysis.

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Influenza della sostanza organica policarbossilica sulla tossicità di triorganostagno in ambienti marini. Effetti modulanti del poliacrilato sulla tossicità del trimetilstagno (IV) in immunociti di Paracentrotus lividus.

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Interaction of the Dioxouranium(VI) Ion with Aspartate and Glutamate in NaCl(aq) at Different Ionic Strengths

The formation of complexes species of the dioxouranium(VI) ion with aspartic and glutamic acids was studied in the pH range of 3 to 6 at 25 °C by potentiometric measurements (H+−glass electrode). R...

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Sequestration of toxic metal ions and organometallic cations by poly-electrolyte ligands

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Chemical speciation of organic matter in natural waters. Interaction of nucleotide 5′ mono-, di- and triphosphates with major components of seawater

AbstractThe interactions of nucleotide 5’ mono-, di- and triphosphates in a multicomponent ionic medium simulating the macro-composition of seawater (Na+, K+, Ca2+, Mg2+, Cl-, SO42-, Synthetic Sea Water, SSW) have been investigated at different ionic strengths and at T= 25°C. A chemical speciation model, according to which all the internal interactions between the components of the ionic medium are taken into account, was applied to determine the effective formation constants of species in the nucleotide-seawater system. The results were compared to protonation parameters calculated from single electrolyte systems. A simpler model (SSW considered as a single salt BA, with Bz+ and Az-), repr…

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Thermodynamic Study For The Protonation Of Halloysite

The Halloysite (Al2Si2O5(OH)4·2H2O) is an abundant and cheap clay and is considered one of the most promising nano structured and naturally occurring clay mineral. Large deposits of this material are present in France, Belgium, China, New Zealand and USA [1,2]. Among the spheroidal, tubular or platy morphologies, the tubular is the most common and abundant one. Typically, halloysite nanotubes (HNTs) are formed by 15 – 20 aluminosilicate layers, having a length of 1 ± 0.5 μm, and inner and outer diameters of 10 – 15 nm and 50 -70 nm, respectively [1]. In each layer, the SiOH and the AlOH groups are disposed on the external and the internal surfaces, respectively. As consequence, in each nano…

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Solubility of some calcium-carboxylic ligand complexes in aqueous solution

Insoluble species were identified in the systems Ca(2+)-hemimellitate, Ca(2+)-1,2,3,4-butanetetracarboxylate and Ca(2+)-citrate, and their solubilities were determined in aqueous solution at T = 25 degrees C. Values of pK(s0) were obtained for the species CaLH (L = benzene-1,2,3-tricarboxylate or hemimellitate), Ca(2)L (L = 1,2,3,4-butanetetracarboxylate), CaLH and Ca(3)L(2) (L = citrate), together with their dependence on ionic strength. Solid compounds were also characterized by thermogravimetry. The complex formation in solution for the system Na(+) - and Ca(2+)-hemimellitate was studied too.

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Pb(II) adsorption by a novel activated carbon - alginate composite material. A kinetic and equilibrium study.

The adsorption capacity of an activated carbon – calcium alginate composite material (ACAA-Ca) has been tested with the aim of developing a new and more efficient adsorbent material to remove Pb(II) ion from aqueous solution. The study was carried out at pH = 5, in NaCl medium and in the ionic strength range 0.1–0.75 mol L−1. Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique was used to check the amount of Pb(II) ion removed during kinetic and equilibrium experiments. Different kinetic (pseudo first order, pseudo second order and Vermuelen) and equilibrium (Langmuir and Freundlich) models were used to fit experimental data, and were statistically compared. Calcium alginate …

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Interaction of Dioxouranium(VI) ion with aspartate and glutamate in NaClaq at different ionic strengths

The formation of complexes species of the dioxouranium(VI) ion with aspartic and glutamic acids was studied in the pH range of 3 to 6 at 25 °C by potentiometric measurements (H+-glass electrode). Results gave evidence for the formation of the following species: (UO2)A0, (UO2)AH+, and (UO2)2A(OH)2 0 (A2- ) a glutamic or aspartic ligand). Investigations were carried out in a NaCl ionic medium at I (0.1, 0.25, 0.5, and 1.0) mol L-1. The dependence on ionic strength of the formation constants was analyzed by the specific ion interaction theory (SIT) model. The formation constants at infinite dilution, obtained using this model, are log â110 ) 8.53 ( 0.03, 8.37 ( 0.05; log â111 ) 13.60 ( 0.05, 1…

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Polycyclic Aromatic Hydrocarbons (PAH) in Volcano island (Aeolian archipelago) mud utilized for therapeutic purpose

This paper examines the possible presence, distribution, nature and sources of 18 Polycyclic Aromatic Hydrocarbons (PAH) as constituents of the mud pools collected in Vulcano Aeolian Island. PAH are important from environmental and toxicological point of view. Analysis was performed by gas chromatography/mass spectrometry (GC/MS) in selected ion monitoring (SIM). The total concentration of Polycyclic Aromatic Hydrocarbons ranged from 112 to 154 μ g/Kg of dry matrix. The volcanic mud, used for therapeutic purposes, are moderately contaminated.

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Formazione di complessi di Cu(II) e Cd(II) con leganti policarbossilici. Studio potenziometrico con ISE-H+, ISE-Cu2+ e ISE-Cd2+.

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A critical approach to the toxic metal ion removal by hazelnut and almond shells

The adsorption capacity of ground hazelnut (HS) and almond (AS) shells towards Pb(II) and Cd(II) has been studied at pH = 5, in NaNO3 and NaCl ionic media, in the ionic strength range 0.05-0.5 mol L-1. Kinetic and equilibrium experiments were carried out by using the Differential Pulse Anodic Stripping Voltammetry technique to check the amount of the metal ion removed by HS and AS materials. Different kinetic and equilibrium equations were used to fit experimental data and a statistical study was done to establish the suitable model for the data fitting. A speciation study of the metal ions in solution was also done in order to evaluate the influence of the ionic medium on the adsorption pr…

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Enhancement of Hydrolysis through the Formation of Mixed Heterometal Species: Al3+/CH3Sn3+ Mixtures

ABSTRACT: The hydrolysis of mixed-metal cations (Al3+/CH3Sn3+) was studied in aqueous solutions of NaNO3, at I = 1.00 ± 0.05 mol·dm−3 and T = 298.15 K, by potentiometric technique. Several hydrolytic mixed species are formed in this mixed system, namely, Alp(CH3Sn)q(OH)r with (p, q, r) = (1, 1, 4), (1, 1, 5), (1, 1, 6), (2, 1, 4), (1, 2, 5), (1, 4, 11), (1, 3, 8), and (7, 6, 32). The stability of these species, expressed by the equilibrium: pAl3+ + qCH3Sn3+ + rOH− = Alp(CH3Sn)q(OH)r 3(p+q)−r, βpqr OH, can be modeled by the empirical relationship: log βpqr OH = −3.34 + 2.67p + 9.23(q + r). By using the equilibrium constant Xpqr relative to the formation reaction: pAl(p+q)(OH)r + q(CH3Sn)(p+q…

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Protonation thermodynamics of 2,2'-bipyridyl in aqueous solution. Salt effects and weak complex formation

Abstract Protonation constants of 2,2'-bipyridyl (bipy) have been determined potentiometrically, using (H + )-glass electrode, in different aqueous media (alkali and alkaline earth chlorides, tetramethylammonium chloride and tetramethylammonium iodide) at different temperatures and ionic strengths. The differences in log K H values are explained using a complex formation model. Formation thermodynamic parameters are given.

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Advances in the investigation of dioxouranium(VI) complexes of interest for natural fluids

Abstract The interactions of dioxouranium(VI) cation with different organic and inorganic ligands of environmental and biological interest were carefully examined with the aim to draw a chemical speciation picture of this ion in natural aquatic ecosystems and in biological fluids. Since UO22+ ion shows a significant tendency to hydrolyze, particular attention was paid in considering the hydrolysis species formation both in the presence and in absence of ligands. The results reported in the literature show that formation of the hydrolytic species assumes a great importance in the complexation models for all the UO22+-ligand systems considered. In particular, the following ligands have been t…

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Interazioni UO2 – ATP in soluzione acquosa

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Capacità sequestrante di leganti policarbossilici naturali e di sintesi nei confronti dello ione (CH3)Hg+

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