Voltammetric Investigation on Uranyl Sorption by Alginate Based Material. Influence of Hydrolysis and pH Dependence

The removal of U(VI) as uranyl (UO22+) from aqueous solutions was investigated by sorption onto alginate based material. The hydrolysis of uranyl ion was always taken into account in the calculations of free (22UO) ion in aqueous solution, in the experimental pH range considered, as well as the acid-base properties of alginate polymer. The sorption process follows a pseudo-second order kinetic model and the sorption rate decreases when the pH value increases. In addition to the classical Langmuir and Freundlich models, the equilibrium data were fitted by using a modified multi-component equilibrium model, never tested before. Differential Pulse Voltammetry (DPV) and Inductively Coupled Plas…

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…

Monitoraggio di gas anestetici in sale operatorie di Palermo e provincia

Geochemical mobility of toxic elements in soil and sedimets from Sicily

Combination of different advanced oxidation processes and activated carbons for treatment of salt water

Bilgewater is a corrosive polluted effluent from the bilge of ships that mainly originates from seawater infiltration and leakage of engine oil and fuel. Each year, thousands tons of hydrocarbons from bilge are discharged at sea. In order to prevent hydrocarbon discharge at sea from the bilge of ships, the Internation Maritime Organization (IMO) enacted the MARPOL 73/78 convention in which effluents are now limited to those with maximun oil content of 15 ppmv.

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…

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

Electrospray ion mobility mass spectrometry of positively and negatively charged (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide aggregates

Rationale Self-assembling processes of surfactants in the gas phase constitute a developing research field of interest since they allow information to be gained on the peculiar structural organization of these aggregates, on their ability to incorporate from small molecules up to proteins and on their possible use as carriers of drugs in the gas phase or as cleaning agents and exotic reaction media. Methods The mass spectra of charged aggregates of the chiral surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2-phenylethyl)dimethylammonium bromide (DMEB) in the gas phase have been recorded using a Synapt G2-Si mass spectrometer in the positive and negative ion mode. For comparison purposes, the …

Preliminary evaluation of biopolymers production by mixed microbial culture from citrus wastewater in a MBR system using respirometric techniques

Abstract This preliminary study was aimed at evaluating the feasibility to produce biopolymers (BP) from citrus wastewater by mixed microbial culture in an anaerobic/aerobic membrane bioreactor (A/O-MBR). The activated sludge of the A/O-MBR was successfully enriched in microorganisms having a good capacity in producing intracellular biopolymers. The production of BP was found to be about 0.55 mgCOD mgCOD−1 using pure acetate at a concentration of 1000 mgCOD L−1. When using fermented wastewater, the conversion of acetate into BP product was 0.56 mgCOD mgCOD−1 in the test performed with C/N equal to 1000:1, whereas it was only 0.12 mgCOD mgCOD−1 in the test with C/N of 100:5. The results achi…

Co-inertia multivariate approach for the evaluation of anthropogenic impact on two commercial fish along Tyrrhenian coasts

Abstract Aliphatic hydrocarbon levels were determined by the GC/MS technique in fish livers of Engraulis encrasicolus (Ee) and Trachurus trachurus (Tt), collected from a particular area of the Mediterranean Sea, called GSA 10, which is located exactly in Tyrrhenian Sea between Campania coast and North Sicily coast. The aim was to evaluate their potential use as specific bioindicators towards this class of contaminants. Both Tt and Ee are considered to be pollution monitoring bioindicators, due to their dominance in marine communities and economic fishing interest. Ee showed a higher tendency to bioaccumulate TAHs, due to the lower quantity of fatty acids in liver tissues with respect to Tt.…

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…

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…

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…

Micelles, Rods, Liposomes, and Other Supramolecular Surfactant Aggregates: Computational Approaches

Surfactants are an interesting class of compounds characterized by the segregation of polar and apolar domains in the same molecule. This peculiarity makes possible a whole series of microscopic and macroscopic effects. Among their features, their ability to segregate particles (fluids or entire domains) and to reduce the surface/interfacial tension is the utmost important. The interest in the chemistry of surfactants never weakened; instead, waves of increasing interest have occurred every time a new field of application of these molecules has been discovered. All these special characteristics depend largely on the ability of surfactants to self-assemble and constitute supramolecular struc…

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...

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…

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

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.

Hg and Se exposure in brain tissues of striped dolphin (Stenella coeruleoalba) and bottlenose dolphin (Tursiops truncatus) from the Tyrrhenian and Adriatic Seas.

In this study we analyzed Hg and Se concentrations in dolphin brain tissues of fifteen specimens of striped dolphin (Stenella coeruleoalba) and eight specimens of bottlenose dolphin (Tursiops truncatus) stranded in the Tyrrhenian and Adriatic Seas, in order to assess the toxicological risks associated with Hg exposure. High Hg concentrations were found in brain tissues of both analyzed specie (1.86–243 mg/kg dw for striped dolphin and 2.1–98.7 mg/kg dw for bottlenose dolphin), exceeding levels associated with marine mammals neurotoxicity. Althougth the results clearly suggest that the protective effects of Se against Hg toxicity occur in cetaceans’ brain tissues, a molar excess of mercury w…

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…

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…

Evaluation and comparison of trace metal accumulation in different tissues of potential bioindicator organisms: Macrobenthic filter feedersStyela plicata, Sabella spallanzanii, andMytilus galloprovincialis

Trace metal concentrations were measured in different tissues of Sabella spallanzanii, Styela plicata, and Mytilus galloprovincialis collected in the Termini Imerese Harbor (Sicily, Italy) to evaluate the potential use of these species as bioindicators. Higher bioaccumulation factors (BAFs) were calculated in the tube of S. spallanzanii, except for As, which had a higher BAF in the branchial crown of the same species. Regarding the other species analyzed, higher BAFs were found in the digestive gland of M. galloprovincialis. An exception was Pb, which was significantly more concentrated in the branchial basket and tunic of S. plicata. The BAFs calculated in the present study show that all t…

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

Trace element fractionation through halite crystallisation: Geochemical mechanisms and environmental implications

Halite is an important mineral for industry, agriculture and food production. It crystallises after water evaporation, while the progressive growth of dissolved metal ions in brines is occurring. Then, halite exploitation may provide the delivery of metal ions in the environment and the mechanism of this trace element accumulation should be studied. In this work we investigate the distribution of lanthanides and Y (hereafter named Rare Earth Elements, REE), Zr and Hf between crystallising halite and brines in the Dead Sea as geochemical tools for recognising the mechanism of metal ion removal from brines and accumulation in halite. Halite forms cubic crystals where octahedral planes sometim…

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+…

Electrospray Ion Mobility Mass Spectrometry of positively and negatively charged (1R,2S)-Dodecyl(2-hydroxy-1-methyl-2-phenyl-ethyl)dimethylammonium bromide aggregates

RATIONALE: Self-assembling processes of surfactants in the gas phase constitute a developing research field of interest since they allow information to be gained on the peculiar structural organization of these aggregates, on their ability to incorporate from small molecules up to proteins and on their possible use as carriers of drugs in the gas phase or as cleaning agents and exotic reaction media. METHODS: The mass spectra of charged aggregates of the chiral surfactant (1R,2S)-dodecyl(2-hydroxy-1-methyl-2- phenylethyl)dimethylammonium bromide (DMEB) in the gas phase have been recorded using a Synapt G2-Si mass spectrometer in the positive and negative ion mode. For comparison purposes, t…

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…

Zirconium and hafnium fractionation and distribution of Rare Earth Elements in neutral–alkaline waters: Case study of Lake Van hydrothermal system, Turkey

International audience; We investigated the distribution of Zr, Hf, and rare earth elements (REE) as the sum of lanthanides plus Y in the hydrothermal system in the Lake Van area of south-eastern Turkey. This system is characterised by water with variable pH in alkaline conditions resulting from hydrothermal CO2 upraise and neoformation of calcite minerals in near equilibrium with the interacting waters. Zr, Hf, and REE determinations were carried out for aqueous phases and suspended solids in lake water and surrounding thermal springs. We found that dissolved Hf is partitioned relative to Zr during calcite formation and that such fractionation is a function of the Ca2+ activity in warm wat…

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

Sequestration of Organometallic Compounds by Poly –Acrylic Ligands

Effect of a co-substrate supply in a MBR treating shipboard slop: Analysis of hydrocarbon removal, biomass activity and membrane fouling tendency

The paper reports the main results of an experiment carried out on a membrane bioreactor (MBR) plant designed for the treatment of shipboard slops. With a view of a co-treatment process of the slop with other wastewaters, sodium acetate, as external co-substrate, was supplied (high dosage – Period 1, low dosage – Period 2) to evaluate its effects on hydrocarbons removal. The MBR pilot plant enabled approximately 99% of total petroleum hydrocarbon (TPH) removal during the entire experiment, confirming the robustness of the MBR technology for the treatment of slops. The chromatography/mass spectrometry analysis showed that the removal efficiency for each alkane was close to the value observed…

Evaluation and comparison of trace metals accumulation in different tissues of potential bioindicator organisms: Macrobenthic filter feeders Styela plicata, sabella spallanzanii and Mytilus galloprovincialis

Trace metal concentrations were measured in different tissues of Sabella spallanzanii, Styela plicata and Mytilus galloprovincialis collected in Termini Imerese harbor, located in Sicily (Italy), in order to evaluate the potential use of these species as bioindicators. The higher bioaccumulation factors (BAFs) were calculated in tube of Sabella spallanzanii, except for As which shows the higher BAF in branchial crown of the same specie. Regarding the other species analyzed, higher BAFs were found in the digestive gland of Mytilus galloprovincialis. An exception is represented by Pb that is significantly more concentrated in branchial basket and tunic of Styela plicata. The BAFs here calcula…

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…

A multidisciplinary approach to study the “survaiving” of the bioclastic poket beach in highly anthropized areas. The case of Mondello bay (Palermo, Italy).

HPLC/HRMS and GC/MS for Triacylglycerols Characterization of Tuna Fish Oils Obtained from Green Extraction

Background: Fish oil is one of the most common lipidic substances that is consumed as a dietary supplement. The high omega-3 fatty acid content in fish oil is responsible for its numerous health benefits. Fish species such as mackerel, herring, tuna, and salmon are particularly rich in these lipids, which contain two essential omega-3 fatty acids, known as eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Objectives: Due to the scarcity of information in the literature, this study aimed to conduct a qualitative and quantitative characterization of triglycerides (TAGs) in crude tuna fish oil using HPLC/HRMS. Fatty acid (FA) determination was also performed using GC/MS. The tuna fis…

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

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

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

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…

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…

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…

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 …

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…

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…

Metal distribution in organic and inorganic fractions of soils from Sicily

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…

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

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…

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

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…

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…

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

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

Edible Insects an Alternative Nutritional Source of Bioactive Compounds: A Review

Edible insects have the potential to become one of the major future foods. In fact, they can be considered cheap, highly nutritious, and healthy food sources. International agencies, such as the Food and Agriculture Organization (FAO), have focused their attention on the consumption of edible insects, in particular, regarding their nutritional value and possible biological, toxicological, and allergenic risks, wishing the development of analytical methods to verify the authenticity, quality, and safety of insect-based products. Edible insects are rich in proteins, fats, fiber, vitamins, and minerals but also seem to contain large amounts of polyphenols able to have a key role in specific bi…

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

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+…

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 +…

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),…

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…

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

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)

Study of [2-(2’-pyridyl)imidazole] complexes to confirm two main characteristic thermoanalytical behaviors of transition metal complexes based on imidazole derivatives

Abstract Imidazole derivative ligands are recognized as useful models for biomimetic complexes. Among the inorganic–organic hybrid complexes, those with derivatives of imidazole heterocyclic N-donor ligands are interesting for their framework. In previous studies of complexes with imidazole derivative ligands, our group reported two main thermally induced decomposition behaviors supporting two different systematic decomposition trends. In this work, one of these characteristic decomposition mechanisms was again found. The final goal of these serial studies is the possibility to provide, by the experimental evidences, a prediction model of thermal stability and decomposition typical behavior…

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…

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…

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…

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…

One-Pot Analysis: a New Integrated Methodology for Determination of TAG and FA Determination through LC/MS and in-silico Saponification

Vegetable oils differ significantly for their lipid profile and are mainly constituted by triacylglycerols (TAGs). These are esters formed bonding glycerol to three fatty acids (FAs). To the best of our knowledge, FA and TAG profiles in oils and fats are obtained using at least two different experimental techniques. In particular, FA determination requires elaborated procedures for sample preparation and analyte derivatization. In this work, we propose a one-pot analysis able to determine both TAG and FA contents of edible oils, using experimental data obtained from a simple liquid chromatography/mass spectrometry determination of TAGs. This experimental procedure is followed by an in silic…

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…

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

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…

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…

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…

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…

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…

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

Untreated Opuntia ficus indica for the Efficient Adsorption of Ni(II), Pb(II), Cu(II) and Cd(II) Ions from Water

The raw cladode of Opuntia ficus indica (OFI) was evaluated as a sustainable biosorbent for the removal of heavy metals (Ni, Pb, Cu, and Cd) from aqueous solutions. The functional groups of OFI were identified by employing DRIFT-FTIR and CP-MAS-NMR techniques before and after contact with the ions in an aqueous media, showing a rearrangement of the biomass structure due to the complexation between the metal and the functional groups. The adsorption process was studied in both single- and multi-component systems under batch conditions at different pHs (4.0, 5.0, and 6.0), different metal concentrations, and different biomass amounts. The results show that the raw OFI had a removal capacity a…

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.

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

Combination of advanced oxidation processes and active carbons adsorption for the treatment of simulated saline wastewater

Abstract In the present work, an integrated process combining three different technologies, i.e. heterogeneous photocatalysis, homogeneous ozonation and adsorption on granular activated carbon (GAC) was used for the treatment of a synthetic solution simulating saline wastewater. The synergistic effects between the different methods enhance the oxidation rate of the organic compounds in the integrated process, so that its use may result sustainable. It has been found that a relatively low oxidation rate is sufficient to obtain the highest synergy between the three technologies and to maximize the performances. In particular, coupling ozonation and photocatalysis resulted in 20% enhancement i…

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…

Response of Sabella spallanzanii to multiple stressors. The combined effect of infection and copper sulphate

The aim of this work is to study the immune responses of the polychaete Sabella spallanzanii after exposure to copper sulphate, an immunomodulating agent in marine organisms, and the multiple stresses caused by Escherichia coli infection, to validate the species as a model organism in marine-coastal biomonitoring programmes. Polychaetes were housed in laboratory and divided into five experimental groups: 1. Control (no microinjected), 2. filtered seawater + TBS injection (control of point 3), 3. filtered seawater + E. coli injection (control of point 4), 4. CuSO4 + TBS injection (control of point 5), and 5. CuSO4 + E. coli injection. The immune variables, esterase and alkaline phosphatase a…

Optimization of coupled advanced oxidation processes and activated carbons for purification of salt water

Photocatalysis, ozonation and activated carbons were investigated separately and in combination as tools for the purification of polluted salt water. Coupling different processes enables to overcome many drawbacks related to the use of the single technologies and at the same time to exploit possible synergistic effects. In this work a kinetic analysis was performed for modelling the degradation of 4-nitrophenol (4NP) as a probe pollutant molecule in synthetic seawater. Thus, the optimum synergistic conditions of the three processes acting together were determined and discussed.

Bioplastics: A new analytical challenge

Even though petroleum-based plastics are advantageous in complying with the performance requirements in many applications, these are related, throughout their life cycle, to several environmental problems, including greenhouse gas emissions and persistence in marine and terrestrial environments. Therefore, the preservation of natural resources and climate change is considered worldwide, the main reason for which is necessary to reduce consumption and dependence on fossil-based materials. Biopolymers (PLA, PHAs, etc.) are examples of plastics whose use is grown exponentially over the years because of the improvements of their physical and mechanical properties using additives of various natu…

The ascidian Styela plicata hemocytes as a potential biomarker of marine pollution: In vitro effects of seawater and organic mercury.

Toxic metals, such as mercury, contribute substantially to anthropogenic pollution in many estuarine environments. Animals living in those environments, particularly invertebrate filter feeders like tunicates, can be used as bioindicators. In an attempt to identify cellular markers for revealing pollution, this study examined in vitro the effects of different concentrations of methyl mercury on Styela plicata hemocytes. The harvested hemocytes from S. plicata that were exposed to the metal had a significant mortality, cellular count and morphometric alterations. These findings provided evidence of MeHg immunotoxic effects on S. plicata, resulting in hemocyte death and morphological changes …