Sorption of benzene derivatives onto a humic acid-zeolitic tuff adduct.

The sorption of some benzene derivatives: o-xylene, toluene, phenol, benzyl alcohol, resorcinol and hydroquinone onto a zeolitic tuff-humic acid adduct (PCT-ImHA) was analysed by batch technique at 25 °C and neutral pH. PCT-ImHA was prepared by binding leonardite-extracted humic acids (HA) to a zeolitic tuff sample rich in phillipsite and chabazite and enriched with Ca2+ by cation exchange (Ca-PCT). The HA calcium salts were gently mixed with wet Ca-PCT; then, the mixture was heated at 330 °C for 1.5 h. An adduct with almost 2% of HA was obtained. The experimental data were well fitted by the Langmuir adsorption isotherm and showed that saturation capacity (qMax) increased with the octanol-water repartition coefficient (KO-W). The comparison with previous data on sorption onto immobilised HA highlights that qMax values for PCT-ImHA are far higher than the sum of the contributions of the two separate components.

Modelling the biphasic sorption of simazine, imidacloprid, and boscalid in water/soil systems.

The sorption kinetics of simazine (6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine), imidacloprid (1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine), and boscalid (2-chloro-N-(4'-chlorobiphenyl-2-yl)nicotinamide), three pesticides of wide use in agriculture, was determined in five different water/soil systems over a time interval from the initial few seconds to about 1 month. In all the experiments, sorption kinetics showed a biphasic pattern characterized by an initial, relatively short phase with a high sorption rate and a later phase with much a lower sorption rate. Initial sorption capacity increased with soil organic carbon content and with sorbate hydrophobicity. We postulate that the first phase of the process involves a fast second-order sorption reaction on superficial sites of soil particles, whereas the second phase depends on diffusion-controlled migration to internal binding sites. A kinetic equation based on this hybrid model accurately fitted all data sets. Less satisfactory results were obtained employing the pseudo-first order, pseudo-second order, Elovich, two site non-equilibrium, or Weber-Morris equation. The superior performance of the hybrid model for describing boscalid sorption probably reflects the high hydrophobic character and consequent low diffusion rates of this compound. The accuracy of modelling was in any case strongly dependent on the time interval considered.

Sorption of non-ionic organic pollutants onto a humic acids-zeolitic tuff adduct: thermodynamic aspects.

Sorption isotherms from water solutions for toluene, cyclohexane, o-xylene, benzyl alcohol, phenol and cyclohexanol onto a humic acid-zeolite adduct were determined at 4, 14, 24 and 34 °C and utilized to calculate the isosteric enthalpy (ΔadsHi) and isosteric entropy (ΔadsSi) of the process. For hydrocarbon compounds, toluene, cyclohexane and o-xylene, both ΔadsHi and ΔadsSi were negative, the process was exothermic. In contrast, for hydroxyl compounds, benzyl alcohol, phenol and cyclohexanol, ΔadsHi and ΔadsSi were positive, the increase in entropy possibly reflecting the release of water molecules during sorption. The results suggest that sorption/desorption of either class of compounds could be controlled by operating on the temperature.

Contribution of vehicular traffic and industrial facilities to PM10 concentrations in a suburban area of Caserta (Italy).

PM10 levels have been recorded in the suburban area of Caserta (Italy) from February to October 2012. The daily limit was exceeded in 13 % of the determinations, with no significant difference between weekdays and weekends. Benzo[a]pyrene concentrations were in the range 0.01-0.46 ng/m(3), thus, never exceeding the National Standard. The B(a)P-eq was 0.20 ng/m(3). PM10 peaks were associated with wind from east-northeast. The same was observed for Ca concentrations, whereas no relation with wind direction was observed for organic pollutants. The results point to a local limestone quarry and cement factory as the likely major source of PM10 pollution in the area investigated.

Temporal and spatial distribution of BTEX pollutants in the atmosphere of metropolitan areas and neighbouring towns.

Atmospheric BTEX [benzene, toluene, ethylbenzene, o-xylene and (m + p)-xylene] concentrations have been determined in the Naples metropolitan area (NMA) and in two suburban areas located on the north within about 25 km, during 2006. The pollutants were collected by passive samplers (24-h samplings), and analysed by GC-MS. In all the areas analysed the average atmospheric benzene concentrations were higher than the limit value fixed by the European Union for 2010 and in NMA the average concentration (9.8 microg m(-3)) also exceeded the limit fixed for 2006. High linear correlation coefficients between the average daily concentrations of the different BTEX are indicative of a single major source, most likely the vehicular traffic. The temporal and spatial distribution of BTEX relative concentrations suggest that massive emissions in NMA negatively affect the quality of the air in northern suburban areas, prevalently during the hottest months of the year, probably due to transport by local seasonal winds. The ratios between BTEX daily concentrations showed a clear dependence on the intensity of solar actinic flow, indicating a major role of photochemical processes in the air cleaning from these volatile organic pollutants.

Identification of stationary sources of air pollutants by concentration statistical analysis.

The atmospheric concentrations of benzene, toluene, ethylbenzene and isomeric xylenes (BTEX) in a medium-sized town (S. Maria Capua Vetere, about 32000 inhabitants, Southern Italy) have been determined during working days and weekends in 2006. The procedure used was 24h passive adsorption by samplers distributed throughout the town followed by GC/MS analysis. On a yearly base, the arithmetic mean benzene concentrations were above the limit required by the 2000/69/CE European Directive. The Pearson correlation coefficients of the 24h geometric mean BTEX concentrations were indicative of stationary sources of toluene located in a well circumscribed area of the urban territory, active only during the working days and not officially recognized. The results highlight the effectiveness of the statistical approach used in this study for the identification of pollutant sources.

Catalytic effect of dissolved humic acids on the chemical degradation of phenylurea herbicides.

BACKGROUND: Although biodegradation seems to be the main cause of herbicide degradation, abiotic degradation can also be important for chemicals such as phenylureas, which are subject to catalysed soil reactions. The aim of this work is to investigate the effect of dissolved humic acids (HAs), normally present in natural waters, on the hydrolysis of phenylurea herbicides, and it presents a kinetic model that takes into account the role of adsorption. RESULTS: The linearity of the adsorption isotherms indicates that phenylurea-humic acid interaction can be considered in terms of a repartition-like equilibrium of phenylurea between water and HAs. Kinetic experiments show that the degradation rates of phenylureas increase with HA concentration. CONCLUSION: The kinetic equation adopted adequately describes the experimental data trend, allowing the evaluation of the catalytic effect of HAs on the chemical degradation of phenylureas. Carboxyl groups of HAs seem to play a leading role in the catalysis. The kinetic equation derived in this work could be helpful in predicting the persistence of phenylureas and of related compounds in natural water.

Background atmospheric levels of aldehydes, BTEX and PM10 pollutants in a medium-sized city of southern Italy.

Background atmospheric levels of aldehydes, BTEX and PM10 pollutants were measured in the suburb of Caserta (Italy), 75 thousands inhabitants, 41degrees 04' N, on rainless weekdays and weekends during 2005. On weekdays the average daily concentrations (microg m(-3)) were 41.6 PM10, 8.6 benzene, 25.2 toluene, 6.3 ethylbenzene, 14.0 (m+p)-xylene, 11.7 o-xylene, 6.5 formaldehyde, 3.3 acetaldehyde. All the pollutant concentrations were strictly correlated (mean correlation coefficients = 0.90). At weekends the concentrations were lower by about 1.6 times. Both on weekdays and at weekends the PM10 and benzene levels exceeded the limits set by the EU Directive 30/1999 and 69/2000, respectively.

Contribution of air-proof doors and windows to asthma in Campania Plain (Italy).

The relation between the prevalence of doctor-diagnosed asthma in children and the presence of air-proof doors and windows (doors and windows with rubber gaskets) in their homes was investigated by a cross-sectional survey in the area of Campania Plain, South Italy. Information on the occurrence of asthma and home/family characteristics, including parental smoking habit and level of education, was obtained by a questionnaire given to school children, aged 8-14 years, and their parents. After possible confounders were controlled, the risk of developing asthma was found to be significantly higher in children living in houses equipped with air-proof doors and windows (Odds ratio = 1.30, 95% Confidence interval = 1.1-1.5). By reducing the air exchange, these fixtures are likely to produce increased levels of indoor pollutants. No interaction was found between the two variables 'air-proof doors and windows' and 'parental smoking habit'.

Determination of the microscopic rate constants for the hydrolysis of diuron in soil/water mixture.

A kinetic equation for the analysis of the degradation reaction of xenobiotic molecules in the soil/water mixture has been derived. By means of this equation we have evaluated the microscopic rate constant for the abiotic hydrolysis of the herbicide diuron in the water phase of a soil/water mixture assuming that the reaction occurs only in the water phase and that diuron is reversibly adsorbed by the soil with a higher rate. The soil catalytic capacity on the hydrolysis of diuron was evaluated.

Kinetics of the chemical degradation of diuron.

The influence of pH and buffer concentration on the chemical degradation of diuron in water has been analysed over a wide temperature range. The process irreversibly gives 3,4-dichloroaniline as the only product containing the phenyl ring. H+, OH- and phosphate buffer are efficient catalysts of the reaction. The rate constant first increases rapidly at low buffer concentrations and then gradually levels off at higher ones. At 40 degrees C and high phosphate concentration (>0.01 M), or in the extreme pH regions, the half-life is approximately 4 months and the activation energy is 127 +/- 2 kJmol(-1).