Leaching of mecoprop and dichlorprop in calcareous soil. Effect of the exogen organic matter addition in this process.

Leaching studies of mecorprop (R,S)-2-(4-chloro-2-methylphenoxy)propanoic acid, and dichlorprop, (R,S)-2-(4-chloro-2,4-dichlorophenoxy) propanoic acid, under saturated conditions were conducted in unamended and amended soil columns. The purpose of the study was to investigate the leaching of these herbicides in three type of soils and the exogen organic matter effect on this process. The leaching patterns could be related to variation in the soil texture and diffusion processes of the herbicides into micropores within the walls of conducting pore. The leaching rate in the amended soil columns decreased with the addition of organic matter. The breakthrough curves (BTC) of these herbicides in the leachates of the amended soil columns were wider and more diffused than the BTC obtained for the corresponding unamended soil. The theoretical BTC overestimated the pore volume required for the displacement of these pesticides from the soil column. This may be due to the differences in the adsorption process between the bacth and soil columns methods.     

Butyltin occurrence and risk assessment in the sediments of the Iberian Peninsula

The occurrence of butyltin (BT) compounds in more than 50 recent sediment samples of the Iberian Peninsula, collected in the harbours of the western Mediterranean Sea (Spain) and the North Atlantic Ocean (Portugal), including domestic and industrial sewage disposal sites, has been assessed. The highest levels of tributyltin (TBT) (7673 μg kg^?1 dry wt.) were detected in commercial harbours associated with inputs from large vessels. However, relatively high TBT values (about 2150 μg kg^?1 dry wt.) were also detected in fishing and recreational boating areas. Spanish marinas and harbours are more polluted in terms of TBT (5–7673 μg kg^?1 dry wt.) compared to those in Portugal (4–12 μg kg^?1 dry wt.). Generally, the Mediterranean sediments show a BT distribution characterized by the predominance of TBT over the degradation products dibutyl (DBT) and monobutyltin (MBT), indicating the presence of recent inputs, in contrast to the Portuguese coastal distribution. Calculation of butyltin degradation indexes (BDI) confirmed a different trend, depending on the area. Furthermore, a comparative study of the occurrence of BT in different sewage sludge disposal sites shows that domestic primary sewage sludge effluents can contribute to coastal BT pollution, but to a lesser extent when compared with harbours. Historical trends (1995–2003) for Barcelona harbour reveal that BT regulations on the use of TBT-based antifouling paints have not been fully effective. Finally, a comparison against the existing sediment quality guidelines (SQGs) indicated that acute toxic effects could only be expected for TBT in some Mediterranean harbours; conversely, in every North Atlantic Ocean station, a lesser environmental threat for the harbour benthic community is expected.     

Comprehensive study on dioxin contents in binder and anti-caking agent feed additives

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in some additives widely employed as binder and anti-caking agents in feedstuffs, such as kaolin, bentonite, zeolite, etc. with an special attention on sepiolite samples. Owing to their physico-chemical properties, the little information of these materials reported in the literature, the variability of PCDDs/PCDFs found in a preliminary evaluation and the absence of reference materials highlighted further research needed. Therefore, an extensive study on the analytical procedures based on the classical methods was performed with sepiolite samples. The study includes evaluation of reproducibility and repeatibility. To this end, a series of intra-day and nine inter-day analysis were made. The methodolgy was also assessed against the sample size and series of 12.5, 25, 37.5 and 50 g were analyzed. In all cases, the results confirmed good correlation with the parameters evaluated.     

Metal pollution in Spanish terrestrial ecosystems during the twentieth century

We show here additional biological evidence of the alteration in global biogeochemistry by human activities during the twentieth century. The mineral concentration of herbarium specimens of 24 species of vascular plants and three species of bryophytes collected in North and East regions of Spain have substantially changed throughout the twentieth century. While V, a proxy tracer of oil pollution, exponentially increased in the last decades, other metals such as Cr, Ba, Sr, Al, Fe, Pb, Cd and Ti increased up to 1960-1970 and started to decrease in 1985-1995, when environmental legal regulations started to be effective. Multivariate principal component analysis showed an overall change in plant elemental concentrations throughout the different decades of the century and a clear separation of vascular plants and bryophytes. Likely important consequences for ecosystem structure and functioning and even for human health may be expected from these changes in mineral concentration.     

Sector analysis of pH values in the northeastern region of Puerto Rico

Acid rain precipitation has become a major environmental concern. Many long-range projects in the United States and Europe are devoted to the problems associated with acid rain pollution. In Puerto Rico, there has been no formal study on acid rain. The rainfall pH values and the air-mass trajectory of the northeastern part of the island of Puerto Rico on the surface were analyzed from January 1998 to December 2000. The air-mass trajectory was classified in five different sectors, according to where it originates. The mean pH value measured during that period showed a tendency toward acidity. The 80% of the air-mass trajectory that arrived at the station occurred in Sector I, with a pH value of 4.30. The lowest pH value measured was 4.16, and it occurred in Sector V, where the air mass originates in the northwest part of the island.     

Sources, distribution and behaviour of methyl tert-butyl ether (MTBE) in the Tamar Estuary, UK

Negligible information is currently available concerning levels of the fuel additive methyl tert-butyl ether (MTBE) in European estuaries or coastal environments. MTBE was measured at selected potentially contaminated harbours and marinas, and throughout an axial transect of the Tamar Estuary, UK. Headspace solid-phase microextraction was used in combination with GC-MS for its determination. MTBE was detected in water samples from all stations at concentrations ranging from a few ng/l to a maximum of 194 ng/l (in a semi-enclosed harbour). Elevated levels were generally associated with motor vehicle and boating activities. The Tamar road and rail bridges provided a major input to the lower estuary, downstream of which conservative mixing appeared depressed, probably through volatilisation and possibly through salting-out. The selected analytical system (using a Carboxen/PDMS fiber) proved both rapid and highly sensitive (with a detection limit of 6 ng/l). During method development, salinity was shown to have a major influence in controlling the extraction efficiency and it was found necessary to adjust salinity in all samples (to 75% saturation) prior to extraction. From these tests, we (for the first time) estimated the Setschenow ("salting-out") constant of MTBE to be 0.11 l/mol.     

Ability of biosolids and a cationic surfactant to modify methidathion leaching. Modelling with pescol

Packed columns were prepared with an agricultural soil to examine the ability of two organic soil modifiers, biosolid and the cationic surfactant tetradecyl trimethyl ammonium bromide (TDTMA), to alter the leaching of the insecticide methidathion. Ion chloride was used as a tracer of water flow and the mathematical model PESCOL was selected to predict the mobility of the insecticide. The biosolid addition (SB column) delayed the breakthrough curves for methidathion with respect to the non-amended soil (S) column. The cationic surfactant TDTMA, alone or combined with the biosolid (SS and SBS) and previously incorporated in the soil column, caused the highest retardation of this pesticide in the soil columns. Theoretical retardation factors (TRf) were similar to the experimental Rf values for the S and SB columns, and predicted the high retention observed in the SBS and SS columns. The simulation with PESCOL predicted the experimental results.     

Supramolecular interactions of humic acids with organic and inorganic xenobiotics studied by capillary electrophoresis

Methodology based on capillary electrophoresis (CE) to study humic acids (HAs)-xenobiotics interactions is proposed. The interactions of HAs with organic and inorganic xenobiotics like paraquat, diquat, p,p(')-DDE, p,p(')-DDT, potassium ferrocyanide, potassium ferricyanide, chloride, 4-nitrocatechol and other organic compounds were studied. They were found to be of different kind depending on the structure of the xenobiotic molecule and on its charge (neutral, positive or negative). Ion binding, hydrogen bonding, van der Waals forces, ligand exchange, hydrophobic and hydrophilic adsorption, charge-transfer complexes and sequestration are some of the different mechanisms proposed to bind inorganic and organic compounds to HAs.It was also observed that some of the pollutants are strongly complexed (bound) only with some of the HA fractions forming quite stable entities of supramolecular kind, which can migrate independently. In addition, the stability constant of HA-Cl (negatively charged species) was estimated to be logk=3.1+/-0.95. In order to explain the interaction between negatively charged HAs and inorganic anions (like Cl(-), [Fe(CN)(6)](3-) and [Fe(CN)(6)](4-)), it is proposed that macropolycyclic polyamine structures are present in HA supramolecules, and that they are responsible for such strong binding.     

A rainwater quality monitoring network: a preliminary study of the composition of rainwater in Galicia (NW Spain)

A network consisting of 17 sampling stations strategically distributed in the geographical area of Galicia (NW Spain) was set up in January 1999 in order to monitorice the ionic rainwater quality in this Spanish region which has an area approximately 29.575 km(2) and a population of 2.8 million. This paper presents the preliminary results of the exploratory study on the ionic rainfall composition in this area during the first year. In each rainwater sample collected chloride, sulphate, nitrite, nitrate, phosphate, sodium, potassium, magnesium, calcium and ammonium were measured, as were pH, conductivity and precipitation-volume. An univariate study according to the location of each sampling site was performed. Multivariate chemometric techniques, such as principal component analysis and cluster analysis, were applied to the complete data set (consisting of 630 observations) in order to elucidate the factors affecting the ionic composition of rainwater.