Assessment of tin and butyltin species in estuarine superficial sediments from Gipuzkoa,Spain

Ten superficial sediments from river estuaries of Gipuzkoa (North Spain) were collected and analyzed for nine metals (including tin, Sn) and butyltin compounds (monobutyltin, MBT; dibutyltin, DBT; tributyltin, TBT). Total metal concentration in the fine fraction (<63 micrometer) of the sediment was determined in aqua regia--hydrofluoric acid extracts by atomic absorption spectrometry. The butyltin species (BTs) were firstly extracted from the sediments with hydrochloric acid-methanol mixture. After derivatization with sodium tetraethyl borate, the organotin compounds were extracted by solid phase microextraction (SPME) in headspace mode. A fiber coated with 100 micrometer poly(dimethylsiloxane) was used for SPME. The organotin species were analyzed by gas chromatography-flame ionization detection. Analysis of the certified reference sediment (PACS-2) shown the suitability of the procedures for determination of metal contents and DBT-TBT species in contaminated sediments. Factorial analysis was used to examine the main sources of metals. Three factors represented more than 89% of the total variance of the metal system, and the Sn was related with Cu-Zn-Pb suggesting the same pollution source. The BTs concentrations in the area were high (TBT ranged from 0.05 to 5.48 mg Sn kg(-1)). The percentage of total butyltin species ( summation operator BTs) respect to the total Sn amount was higher than 4% in all the sediments, showing in the Bidasoa river estuary a remarkable value higher than 20%. Hence, the studied estuarine sediments reflect a pollution that is related with historical industrial and fishing activities of the area.     

Anthropogenic and natural influence on the PM(10) and PM(2.5) aerosol in Madrid (Spain). Analysis of high concentration episodes

Non-mineral carbon is the main component of PM10 and PM2.5 at an urban roadside site in Madrid accounting for more than 50% of the total bulk mass in winter pollution episodes. In these cases a 70-80% of the particle mass is anthropogenic. Particles of crustal/mineral origin contribute significantly to the observed PM10 concentrations, especially in spring and summer. They have also been found in the PM2.5 fraction although secondary particles are the next most important contributor in this size. Long-range transport particle episodes of Saharan dust significantly contribute to exceedence of the new daily limiting PM10 value in the urban network and at nearby rural background stations. This type of long-range transport event also influences PM2.5 concentrations. The crustal contribution can account for up to 67 and 53% of the PM10 and PM2.5 bulk mass in such cases.     

A microcosm approach to assessing the effects of earthworm inoculation and oat cover cropping on CO2 fluxes and biological properties in an amended semiarid soil

We designed a microcosm experiment to assess the influence of inoculation with Eisenia foetida earthworms and the establishment of an Avena sativa cover crop on biological (enzyme activities and labile carbon fractions) soil quality indicators in a soil treated with a composted organic residue, and to determine the contribution of these treatments to carbon dioxide emissions from the soil to the atmosphere of the microcosm. The microcosms were incubated for 53 days under 28 °C/18 °C day/night temperatures. The addition of earthworms and the planting of A. sativa increased dehydrogenase activity of compost amended soil by about 44% after 23 days of incubation. The metabolic potential, calculated as the ratio dehydrogenase activity/water soluble C, was higher in the compost amended soil planted with A. sativa. The highest total amount of CO₂–C evolved occurred in the soil treated with composted residue and earthworms (about 40% of the total amount of CO₂ evolved came from earthworm activity). The planting of A. sativa increased the decomposition rate constant of organic matter in the amended soil but decreased the potentially mineralizable C pool. In conclusion, the establishment of an A. sativa cover crop and the addition of E. foetida to a degraded agricultural soil treated with composted residue were effective treatments for improving the biological and biochemical quality and the metabolic potential of the soil.     

Results and evaluation of the first study of organochlorine contaminants (PCDDs, PCDFs, PCBs and DDTs), heavy metals and metalloids in birds from Baja California, México

Organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p-p'-DDE), heavy metals (Pb, Cd, Zn, Cu), and arsenic were measured in house sparrows (Passer domesticus) and common ground doves (Columbina passerina) from Baja California Sur, México. Concentrations of PCDD/Fs were low, with 21 pg/g for house sparrows, and 7.7 pg/g for common ground doves. Non-ortho-PCB concentrations in house sparrow and common ground doves were 58 and 254 pg/g, respectively, and are within the highest concentrations reported in species that are in the low levels of food webs. The major differences in organochlorine levels between species were found for ortho-PCBs and DDTs. ortho-PCB levels were higher in the seedeater species, whereas DDT levels were higher in the omnivorous species. Heavy metal levels were far below those associated with negative effects.     

Temporal trends of organochlorine contamination in Black Guillemots in Iceland from 1976 to 1996

The levels of several different persistent organochlorines (OCs) in Black Guillemots Cepphus grylle, collected during the summers of 1976-1996 at Breioafj?rour in W-Iceland, were investigated. The levels of about 40 different organochlorines (PCBs, DDTs, chlordanes, toxaphenes, HCH, HCB) were compared with respect to age, sex, fat content, and year of collection. The levels of PCBs correlated very closely with those of DDE, indicating long-range transport as the major source of these contaminants in Iceland, with the ratio PCBs/DDE mostly in the range of 2-5. Unlike the Gyrfalcon Falco rusticolus, the organochlorine levels did not seem to accumulate substantially with age, neither in males nor females. The variation in the levels of OCs at the age of 2 years was even greater than the variation in OC levels over an age range of 12 years. In immature birds the levels of PCBs, DDE, HCB and beta-HCH declined very slowly (T(1/2) from 12 to 20 years) over the years 1976-1996, whereas the levels of alpha-HCH and p,p'-DDT declined much faster. The levels of trans-nonachlor, alpha-chlordane, gamma-chlordane, oxychlordane, and toxaphene did not correlate with the year of collection. As the Black Guillemot is mostly a resident seabird, feeding mainly on small fish and invertebrates, this investigation should give a good indication of the temporal trends of organochlorine pollution at Breioafj?rour, Iceland, during this 20 year period and is likely to reflect baseline trends in the marine environment of the North-Atlantic Ocean.     

Modelling of the life cycle of Chironomus species using an energy-based model

Little is known about the differences between the species of the genus Chironomus relatively to their life cycle strategies. This knowledge is however crucial to fully understand the response of the Chironomus community to field perturbations. Here, we proposed to study four Chironomus species by using an energy-based model to describe growth, emergence and reproduction. We used data from the literature for two species (Chironomus plumosus and Chironomus tentans) and data from our experiments for two other species (Chironomus prasinus and Chironomus riparius). We showed that our model is able to accurately describe the life-history attributes for all the species tested, which suggests that Chironomus species have the same fundamental characteristics (low maintenance energetic costs, isomorphism), which makes possible the building of a common modelling framework to assess effects of toxicants at individual and population level. The species showed a few differences relatively to the parameters of the models with possible consequences when assessing effects of chemicals on Chironomus community. For instance, due to differences in growth parameters, C. riparius population dynamics should be more sensitive to effects on individual growth than C. prasinus or C. plumosus ones.     

A case study of molinate application in a Portuguese rice field: herbicide dissipation and proposal of a clean-up methodology

This study was designed to monitor molinate losses in surface and underground waters during Ordram application in a rice field situated in central Portugal. Water samples were collected from different sites, before, during and about one month and a half after Ordram application. Molinate quantification was based on a solid-phase microextraction (SPME) method followed by gas chromatography with flame photometric detector (GC-FPD) analysis, and led to the conclusion that the herbicide was dissipated in the environment, reaching levels as high as 3.9 microgl(-1) in underground water and 15.8 microgl(-1) in the river receiving tail waters. The feasibility of the application of treatment methodologies based on adsorption or biodegradation as processes to remove molinate from real-world waters was assessed. These methods seem suitable to reduce molinate concentrations to values in the range of the legally recommended limits (<0.5 microgl(-1)).     

Inclusion complexes of alpha- and gamma-cyclodextrins and the herbicide norflurazon: I. Preparation and characterisation. II. Enhanced solubilisation and removal from soils

The interaction of norflurazon with alpha- and gamma-cyclodextrins (CDs) yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution and in the solid state. Apparent stability constants of 50.7+/-1.6 and 37+/-1.7 M(-1) and an increase in herbicide solubility by up to five and fourfold for alpha- and gamma-CD, respectively, were determined from the phase solubility diagrams at 25 degrees C in water. Three processing methods (kneading, spray-drying and vacuum evaporation) were used to prepare norflurazon-CD solid inclusion complexes, which were characterised by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. A high increase in the norflurazon dissolution rate was obtained with all the solid complexes with gamma-CD, but when alpha-CD was used, only the solid system obtained after the vacuum evaporation process showed a higher dissolution rate. This finding is a first step in the development of new, environmentally sound formulations of norflurazon (NFL), due to the capacity for increasing its dissolution rate and hydrosolubility, and thus diminishing the use of organic solvents. On the other hand, the effect of alpha- and gamma-cyclodextrin on the solubility of norflurazon in solution was also considered as a way of modifying its behaviour in the soil environment. Desorption studies of NFL from soils in the presence of alpha- and gamma-cyclodextrin were carried out using a batch equilibration method. The results obtained showed that alpha- and gamma-cyclodextrin greatly increased the removal of norflurazon previously adsorbed, proving the potential use of these CDs for in situ remediation of pesticide-contaminated soils.     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

Use of the aquatic lichen Dermatocarpon luridum as bioindicator of copper pollution: accumulation and cellular distribution tests

Laboratory experiments were conducted to investigate the potential use of the aquatic lichen Dermatocarpon luridum as bioindicator of copper pollution. Lichen thalli were exposed to 0.00, 0.25, 0.50, 0.75 and 1.00 mM copper in synthetic freshwater to solve the problems of metal bioavailability. The mineral composition of this media was prepared so that it corresponded to the ion composition of natural waters in D. luridum ecosystems. Sequential elution procedures using NiCl2 or Na2-EDTA (20 mM) were used to determine the distribution of metals at different cellular sites. The copper concentration extracted from thalli was correlated with pollution intensity, the greater correlation being with the Na2-EDTA extractant. The malondialdehyde concentration in thalli can be used as indicator of copper pollution; however, similar membrane degradation was observed for 0.25 and 0.50 mM copper and for 0.75 and 1.00 mM copper.