Study of metal fractionation in river sediments. A comparison between kinetic and sequential extraction procedures

The extraction kinetic of trace metals (Cd, Cu, Pb, and Zn) in river sediments by four extraction agents was studied. As extractants ammonium acetate, acetic acid, hydroxylamine and EDTA solutions were assayed. These reagents can leach the metals more or less selectively from several metal compartments of sediments. The metal leaching kinetic model permits classification of the metal species in labile and moderately-labile ones. The combination of two or more non specific reagents permits a high characterisation of metal distribution and leachability. The results obtained with this model in four river sediments were compared with data obtained by the SM&T sequential extraction procedure, in order to characterise the chemical nature of leached metal.     

Dissipation of racemic mecoprop and dichlorprop and their pure R-enantiomers in three calcareous soils with and without peat addition

Two racemic herbicides, mecoprop (R,S-MCPP) and dichlorprop (R,S-DCPP), as well as their enantiopure R-forms, were incubated in three calcareous soils at 15 degrees C and 80% of their field capacity to try to elucidate their behaviour in soil and compare the dissipation rates when racemic and enantiopure compounds are used. Quantitation of pesticides is made by HPLC and the R/S ratio by GC-MS. The inactive S-enantiomer from the racemic forms persists longer than the R-forms in silt and sandy loam soils, but for shorter time in the clay loam soil. The pure R-enantiomers, both for MCPP and DCPP, after incubation in soil, are partially converted into their S-forms. In all cases, the dissipation of racemic and pure enatiomeric forms is lower in the clay loam soil than in the silt and sandy loam soils. The R-forms' peristence, in the three soils, is approximately two times lower when they are incubated alone than when they are incubated as racemic compounds. When peat is added, the persistence of these herbicides in the silt and sandy loam soils increases, while in the clay loam soil it decreases. Besides, in the clay loam soil, the enantiomeric ratio (ER) changes from its S-preferential degradation to a preferential degradation of its R-form, so an increase in the persistence of the inactive S-form occurs.     

Application of principal component analysis for the estimation of source of heavy metal contamination in surface sediments from the Rybnik Reservoir

The concentrations of metals, loss of ignition and nutrient (N, P) were determined in the bottom sediments of the Rybnik Reservoir (southern Poland). The mean concentrations of the metals in the bottom sediments were: Cd 25.8 microgram/g, Cu 451.7 microgram/g, Zn 1583.4 microgram/g, Ni 71.1 microgram/g, Pb 118.6 microgram/g, Cr 129.8 microgram/g, Fe 38782 microgram/g and Mn 2018.7 microgram/g. The bottom sediments are very heavily loaded with zinc, manganese, copper, nickel, phosphorus and lead (percentage enrichment factor), and cadmium, phosphorus and zinc (index of geoaccumulation). The increase of cadmium, lead, nickel and zinc concentrations was connected with the inflow of the contaminated water of the river Ruda and long-range transport. The contamination of the reservoir with copper and manganese resulted mainly from atmospheric precipitation. The variability of the bottom sediment loading with metals during the investigations was affected in the first place by changes in the concentration of iron, but also those elements whose concentrations in the bottom sediment were elevated compared to the concentrations in shale--cadmium, nickel and lead.     

Study on the formation and transport of ozone in relation to the air quality management and vegetation protection in Tenerife (Canary Islands)

An experimental study on the formation and transport of ozone in ambient air was performed in Tenerife (Canary Islands) in order to investigate the processes affecting ozone levels and air quality. The special features of Tenerife (prevalence of the trade wind pattern (NE), orography and the specific location of the local ozone sources) permit to quantify the role of the ‘long-range transport from northern latitudes' versus the ‘formation and transport of ozone downwind of the main urban areas' of Tenerife. Levels of O₃, NO₂ and O_X were monitored in different types of environments to achieve this purpose. The results showed that: (1) upwind of the urban areas ozone is mainly transported from the ocean by trade winds, (2) local ozone titration (by NO) and ozone replenishment from the ocean are the main causes of ozone variations in urban and suburban areas, and (3) photochemical ozone production occurs downwind of the urban areas. Photochemical production causes daylight O₃ and O_X levels downwind of urban areas to be frequently (60% and 35% days/year, respectively) higher than upwind of the urban sites (O₃ and O_X excess frequently in the range 5–20 ppbv). Due to the above processes, different daily ozone cycles occur in short distances (<30 km), with maximum O₃ levels during daylight or night depending on the site. Ozone phytotoxicity was assessed by calculating the AOT40 index upwind and downwind of the main urban areas. The critical value for the 5-day-AOT40 index was simultaneously exceeded at the two sites (few times/year) during long-range transport events. During the additional exceedances of the critical value downwind of the urban area, relatively high 5-day-AOT40 values were recorded upwind of the urban site. Thus, long-range transport from northern latitudes may produce relatively high 5-days-AOT40 levels in the oceanic boundary layer. These results are important for the protection of the large number of endemic plants in the Canaries. The conceptual model discussed in this study may be qualitatively applied to other islands which possess features similar to those of Tenerife.     

Photocatalytic degradation of formaldehyde containing wastewater from veterinarian laboratories

The photocatalytic destruction of methanol, formaline (mixture of formaldehyde, methanol and water) and formaline wastes from the preservation of vertinarian physiologic samples has been attempted by two different processes, at high concentrations of reagents and by dossification of reagents, varying pH in both. Experiment evolution has been monitored by measuring the organic matter such as TOC and formaldehyde concentrations [H2CO]. Also, methanol and methanol-formaldehyde interactions with the TiO2 surface have been analysed by FTIR spectroscopy. Results indicate that at high concentrations the catalyst surfacial alterations given by methoxy, formates or carbonates, according to the pH of the sample can profoundly affect catalyst behaviour. It has been established that reagent dossification is advantageous for enhancing photonic efficiency as it minimizes the adsorbate presence that hampers the photocatalytic process.     

Organochlorine compounds in soils and sediments of the mountain Andean Lakes

Semi-volatile organochlorine compounds (OC) were analyzed in remote Andean soils and lake sediments. The sampling sites covered a wide latitudinal gradient from 18 degrees S to 46 degrees S along Chile and an altitudinal gradient (10-4500 m). The concentrations were in the order of background levels, involving absence of major pollution sources in the high mountain areas. Significant correlations were found between log-transformed concentrations of hexachlorobenzene, alpha- and gamma-hexachlorocyclohexane in soils and total organic content (TOC). In addition, TOC-normalized concentrations of the most volatile OC showed a significant linear dependence with air temperature. This good agreement points to temperature as a significant factor for the retention of long range transported OC in remote ecosystems such as the Andean mountains, although other variables should not be totally excluded. The highest concentrations of OCs were achieved in the sites located at highest altitude and lowest temperature of the dataset.     

Kinetics of photodegradation and ozonation of pentachlorophenol

The oxidation of 2,3,4,5,6-pentachlorophenol (PCP) has been carried out by a photodecomposition process using a polychromatic UV irradiation, and by an ozonation process. In the photodegradation process, the pH accelerated the decomposition rate and the approximate first-order rate constants were evaluated, with values between 0.16+/-0.005 min(-1) at pH=3 and 0.26+/-0.007 min(-1) at pH=9. A more rigorous kinetic study led to the determination of the quantum yields of the reaction, with values of 200+/-7x10(-3) mol/Eins for pH=3 and 22+/-1.1x10(-3) mol/Eins for pH=9. In the ozonation process, the rate constants for the reaction between ozone and PCP were determined by means of a competition kinetics, with values in the range from 0.67x10(5) to 314x10(5) l/mols. The specific rate constants for the un-dissociated and dissociated forms of PCP were also calculated. Finally, in both processes, the intermediate reaction products were identified, the most important being tetrachlorocatechol, tetrachlorohydroquinone and tetra-p-chlorobenzoquinone. Free chloride ion released, which was favored at high pHs, was also followed in both processes.     

Carbonyls in the metropolitan area of Mexico City: calculation of the total photolytic rate constants Kp(s(-1)) and photolytic lifetime (tau) of ambient formaldehyde and acetaldehyde

A great number of studies on the ambient levels of formaldehyde and other carbonyls in the urban rural and maritime atmospheres have been published because of their chemical and toxicological characteristics, and adverse health effects. Due to their toxicological effects, it was considered necessary to measure these compounds at different sites in the metropolitan area of Mexico City, and to calculate the total rate of photolytic constants and the photolytic lifetime of formaldehyde and acetaldehyde. Four sites were chosen. Sampling was carried out at different seasons and atmospheric conditions. The results indicated that formaldehyde was the most abundant carbonyl, followed by acetone and acetaldehyde. Data sets obtained from the 4 sites were chosen to calculate the total rate of photolysis and the photolytic lifetime for formaldehyde and acetaldehyde. Maximum photolytic rate values were obtained at the maximum actinic fluxes, as was to be expected.     

Toxic by-products from the combustion of Kraft lignin

Lignin samples, sub-product in the Kraft process of cellulose from eucalyptus wood, were burnt in a laboratory scale furnace at different residence temperatures and with distinct fuel-rich atmospheres. The yields of CO, CO(2), eight light hydrocarbons (methane, ethylene, ethane, propylene, acetylene, butane, etc.) and 60 semi-volatile+volatile compounds (benzene, toluene, ethylbenzene, styrene, indene, naphthalene, dibenzofuran, phenanthrene, chrysene, etc.) were determined, with nominal reactor temperatures between 800 and 1100 degrees C and residence times of the volatiles evolved and formed between 4 and 7 s. The collection of the gases and volatiles evolved was carried out with a Tedlar bag and by XAD-4 resin respectively, comparing the data obtained in both cases. The emission factor (mg/kg) of the CO was between 2500 and 90000, and under the poor-oxygen atmosphere, the emission factors of many by-toxic products were greater than 100 mg/kg. A pyrolysis run was also performed, obtaining emission factors between 30 and 3000 mg/kg, facilitating its identification. The behaviour of different compounds in the combustion runs was discussed considering three groups in accordance with their stability vs. oxygen, and two groups vs. temperature.     

Absorption and translocation of 2,4-D in plants of Memora peregrina

The objective of this work was to evaluate absorption and translocation of the herbicide 2,4-D in plants of Memora peregrina. The herbicide 2,4-D was used alone with the formulation DMA 806 BR and associated with the herbicide picloram in the commercial product Padron. Levels of radioactivity on the treated leaves were determined in sample obtained after washing them with methanol and chloroform at different times after the application of the radiolabelled formulation (1, 2, 4, 8, 24, and 48 h). Translocation was evaluated by cutting plants between stem and root. The parts obtained were: root, stem, leaf treated, leaves above the leaf treated, leaves below the leaf treated, and leaf opposite of the leaf treated. These parts were weighted, dried, ground, burnt, and radioactivity in the samples was determined. The results suggest that the translocation of the radioactive herbicide 2,4-D was insignificant in plants of M. peregrina in the two treatments evaluated. Absorption of 14C 2,4-D in the treatment with DMA 806 BR and the mixture of DMA 806 BR plus Padron had the same behavior. These observations explain the inefficient control obtained with this herbicide in plant species under study.