Antonio Gianguzza

Protonation of carbonate in aqueous tetraalkylammonium salts at 25 °C

Protonation constants of carbonate were determined in tetramethylammonium chloride (Me(4)NCl(aq) 0.1</=I/molkg(-1)</=4) and tetraethylammonium iodide (Et(4)NI(aq) 0.1</=I/molkg(-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 NaCl(aq) (0.1</=I/molkg(-1)</=6) were also critically analysed. Both protonation constants of carbonate follow the trend Et(4)NI>Me(4)NCl>NaCl. An ion pair formation model designed to take into account the different protonation behaviours of carbonate in different supporting electrolytes was also evaluated.

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) were 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 (ΣPAHs) ranged from 74 to 5755 μg/kg of dry matrix. The resulting distributions and molecular ratios of specific compounds are 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 PAHs are homogeneous in most of the sampling stations. The organic matter content and PAH concentration were found to be correlated (r = 0.90). It is also shown that the pyrolytic origin is the main source of these compounds in Ganzirri and Faro Lakes sediments.

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 both in terms of specific interaction and in terms of complex formation. The formation constants of Mg 2+ –glycine complexes have been calculated from protonation data in mixed Na + –Mg 2+ solutions at high ionic strength: a simple method for taking into account the different composition, at constant ionic strength, is reported. The overall complexing ability of major seawater components towards amino acids has been calculated from potentiometric data in artificial seawater using the single salt approximation. The relevance of the data reported in this work is discussed in connection with speciation problems. Particular attention has been paid to finding some useful predictive relationships.

Salt effects on the protonation of ortho-phosphate between 10 and 50°C in aqueous solution. A complex formation model

Protonation constants of o-phosphate were studied potentiometrically, using the (H+)-glass electrode in aqueous NaCl, KCl and tetraethylammonium iodide solutions, at 0≤I≤IM and 10≤T≤50°C. The differences found in the protonation constants for different salt solutions are explained by a complex formation model. The formation of the species MPO42−, MHPO4−, MH2PO40, M2PO4− and M2HPO40 (M=Na+, K+) is hypothesized. In mixed NaCl-KCl solutions, it is possible to find the mixed metal species NaKPO4− and NaKHPO40. Ionic strength and temperature dependence parameters are reported for all species. The relevance of Na+ and K+ complexes is discussed in connection with speciation problems of natural fluids, such as marine water and urine.

Equilibrium studies in natural fluids: a chemical speciation model for the major constituents of sea water

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.

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 + >Na + ≥K + , in accordance with the tendencies of these cations to interact with polycarboxylates. The dependence on molecular weight shows a slightly increasing effect with N (number of monomer units in the polyelectrolyte). Empirical relationships were found for the dependence of the protonation parameters on both ionic strength (I/mol l −1 ) and N. The use of protonation data was considered for polyacrylates in speciation studies, and specific interaction parameters were calculated according to the SIT (Specific Ion Interaction Theory) model.

Salt effects on the protonation and on alkali and alkaline earth metal complex formation of 1,2,3-propanetricarboxylate in aqueous solution

The protonation of 1,2,3-propanetricarboxylate (tricarballylate, tca) was studied in LiCl, NaCl, KCl, MgCl(2), CaCl(2) and tetraethylammonium iodide (Et(4)NI) aqueous solutions, at 25 degrees C, in the ionic strength range 0 < I < 1M, using the pH-metric technique. The differences between protonation constants determined in Et(4)NI and those determined in the other background salts were interpreted in terms of complex formations. Least squares calculations are consistent with the formation of MLH(j) (j = 0,1.2), M(2)LH(i) (i = 0,1,2), M(2)L species, when M = Mg(2+), Ca(2+). Potentiometric measurements performed in mixed NaClKCl, NaClCaCl(2) and MgCl(2)CaCl(2) solutions showed the formation of mixed metal complexes NaKL, NaKHL, NaCaL and CaMgL. The dependence on ionic strength of protonation and complex formation constants was evaluated using a simple Debye-Hückel type equation.

The single salt approximation for the major components of seawater: association and acid–base properties

In this note we propose the use of the single salt approximation for the composition of seawater. This approximation has been applied to a synthetic seawater. Association and acid-base properties h...

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

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 microg/kg (bark dry weight), as SigmaPAHs, at the control site to 1015 microg/kg along a road with high traffic flow.

LEAVES OF NERIUM OLEANDER L. 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 rise to a characteristic PAH pattern, and it is therefore possible to get access to the processes that generate the compounds. To this aim, the recommended as priority pollutants by the Environmental Protection Agency (EPA), perylene and three additional alkylated compounds were analyzed. Positive correlations were found between total PAH content of the leaves with CO, benzene and particulate levels measured in air of Palermo.