Enantiomeric fractions and congener specific determination of polychlorinated biphenyls in eggs of predatory birds from Doñana National Park (Spain)

The content of 30 polychlorinated biphenyls (PCBs) and the enantiomeric fractions of 10 chiral PCBs were determined in 17 infertile eggs from three different predatory bird species collected in Do?ana National Park (DNP, Spain) in the period 1999-2000. The highest PCB concentration was found in eggs from red kites (0.52-110 microg/g on a fresh weight basis, f.w.) followed by buzzard (0.08-13 microg/g f.w.) and booted eagle (0.10-1.5 microg/g f.w.). Seventy-five percent of the red kite eggs had PCB levels above 4.7 microg/g f.w., which is associated in the literature with reproductive failure. This could be related to the fact that red kite populations have decreased by more than 50% in the last five years in DNP. PCBs # 138, 153, and 180 were the most abundant in all cases. This is the first time that atropisomers of 10 chiral PCBs (PCBs # 45, 84, 91, 95, 132, 135, 136, 149, 174, and 176) in predatory bird eggs have been performed. The enantiomeric fractions (EFs) for most PCBs investigated were non-racemic (EF not = 0.5), ranging from 0.05 to 0.95. The results suggested that predatory birds, mainly red kite species, are highly polluted by PCBs, and PCBs # 95, 132, 135, 136, and 174 strongly deviate from the racemic-mixture values.     

Breakdown products on metabolic pathway of degradation of benz[a]anthracene by a ligninolytic fungus

Cultures of the ligninolytic fungus Irpex lacteus incubated in a nutrient liquid medium degraded more than 70% of the initially applied benz[a]anthracene within 14 days. At the first step of metabolization, benz[a]anthracene was transformed via a typical pathway of ligninolytic fungi to benz[a]anthracene-7,12-dione (BaAQ). The product was further transformed by at least two ways, whereas one is complied with the anthracene metabolic pathway of I. lacteus. Benz[a]anthracene-7,12-dione was degraded to 1,2-naphthalenedicarboxylic acid and phthalic acid that was followed with production of 2-hydroxymethyl benzoic acid or monomethyl and dimethylesters of phthalic acid. Another degradation product of BaAQ was identified as 1-tetralone. Its transformation via 1,4-naphthalenedione, 1,4-naphthalenediol and 1,2,3,4-tetrahydro-1-hydroxynaphthalene resulted again in phthalic acid. None of the intermediates were identified as dead-end metabolites. Metabolites produced by ring cleavage of benz[a]anthracene using the ligninolytic fungus are firstly presented in this work.     

Cadmium and zinc bioaccumulation and metallothionein response in two freshwater bivalves (Corbicula fluminea and Dreissena polymorpha) transplanted along a polymetallic gradient

This study was designed to compare the metallothionein (MT) response capacity of two freshwater bivalves, Corbicula fluminea and Dreissena polymorpha, along an environmental gradient of polymetallic pollution. The bivalves were transplanted into 4 stations in southwestern France, with a cadmium and zinc pollution gradient. MT and metal concentrations were measured in the soft bodies of the clams and mussels over 2.5 months. In the zebra mussels, variations in MT concentrations were strictly correlated to progressive Cd and Zn bioaccumulation. In contrast, the faster response in the clams appeared positively correlated to Cd accumulation only, with the activation of efficient detoxification mechanisms which limited Cd bioaccumulation and reduced Zn concentrations over time. Nevertheless, despite stronger metal accumulation factors in D. polymorpha, C. fluminea revealed higher sensitivity of MT response along the pollution gradient.     

In situ and laboratory bioassays using Poecilia reticulata Peters, 1859 in the biomonitoring of an acidic lake at Camaçari, BA, Brazil

The suitability and viability of acute in situ bioassays were investigated in the biomonitoring program of an acidic lake contaminated with sulphur residues. Responses of organisms observed in laboratory and in situ bioassays were also assessed to determine whether or not they were similar and comparable, regarding accuracy and precision. Newborn Poecilia reticulata were employed as test organisms and exposed to the same water samples under in situ and laboratory conditions. Mortality/immobility was the endpoint assessed and dead/immobile organisms were counted at various time intervals during exposure. The mean calculated LT50 values and 95% confidence intervals were 1.61 (1.36-1.87) h in the laboratory bioassays and 0.72 (0.55-0.89) h in the in situ bioassays. Statistical comparison of these values revealed a significant difference (p<0.05). In situ bioassays were more accurate than those carried out in the laboratory, demonstrating higher sensitivity and better reproduction of what occurs in nature, while laboratory bioassays were more precise.     

Effect of 2,4-D contamination on soil functional stability evaluated using the relative soil stability index (RSSI)

Soil functional stability is the capacity of soil functions to resist and recover from an environmental perturbation and can be used to evaluate soil health. It can be influenced by the presence of xenobiotics such as herbicides. The impact of a fresh 2,4-D contamination (36 mg kg(-1) dry soil) on soil functional stability was evaluated by comparing the capacity of soil enzyme activities to resist and recover from a heat perturbation for both a clean and 2,4-D-contaminated soil. The functional stabilities of the soils (uniform sands, pH 6.9, 7% (w/w) organic matter) were calculated using the relative soil stability index (RSSI). The RSSI scores indicate the proportion of potential enzyme activity the soil retains after a perturbation compared to the potential activity of an unperturbed soil. Six extra-cellular enzyme activities (acid and alkaline phosphatases, arylsulfatase, urease, protease and beta-glucosidase) were monitored in soil microcosms during a 15-day period. During this period, a 60 degrees C heat perturbation was applied to the soil for 24 h. The activities of arylsulfatase and protease were found to be the most stable following heat perturbation obtaining the highest RSSI scores (87% and 77%, respectively). Urease activity showed the lowest RSSI score (38%). Although all enzyme activities were inhibited by the presence of 2,4-D, the RSSI results indicated that contamination lowered the stability of only three enzyme activities (arylsulfatase, beta-glucosidase and urease). The RSSI adequately described resistance, recovery and recovery rate parameters and enabled differentiation between functional stabilities of clean and contaminated soil and between different soil types.     

Geochemical variations in aeolian mineral particles from the Sahara-Sahel Dust Corridor

The Sahara-Sahel Dust Corridor runs from Chad to Mauritania and expels huge amounts of mineral aerosols into the Atlantic Ocean. Data on samples collected from Algeria, Chad, Niger, and Western Sahara illustrate how corridor dust mineralogy and chemistry relate to geological source and weathering/transport history. Dusts sourced directly from igneous and metamorphic massifs are geochemically immature, retaining soluble cations (e.g., K, Na, Rb, Sr) and accessory minerals containing HFSE (e.g., Zr, Hf, U, Th) and REE. In contrast, silicate dust chemistry in desert basins (e.g., Bodélé Depression) is influenced by a longer history of transport, physical winnowing (e.g., loss of Zr, Hf, Th), chemical leaching (e.g., loss of Na, K, Rb), and mixing with intrabasinal materials such as diatoms and evaporitic salts. Mineral aerosols blown along the corridor by the winter Harmattan winds mix these basinal and basement materials. Dusts blown into the corridor from sub-Saharan Africa during the summer monsoon source from deeply chemically weathered terrains and are therefore likely to be more kaolinitic and stripped of mobile elements (e.g., Na, K, Mg, Ca, LILE), but retain immobile and resistant elements (e.g., Zr, Hf, REE). Finally, dusts blown southwestwards into the corridor from along the Atlantic Coastal Basin will be enriched in carbonate from Mesozoic-Cenozoic marine limestones, depleted in Th, Nb, and Ta, and locally contaminated by uranium-bearing phosphate deposits.     

Physiological recovery from episodic acid stress does not mean population recovery of Gammarus fossarum

The physiological responses of the acid-sensitive amphipod Gammarus fossarum exposed in situ to acid stress (pH4.5 and 5.5) and then transferred back to neutral water were investigated. Survival rate and haemolymph [Cl(-)] and [Na(+)] were assessed after 24, 48 and 72h of exposure in acidic streams and after a recovery period of 12, 24, 36, 48 and 60h. After 24h, exposure to slightly acidic (pH5.5) and strongly acidic water (pH4.5) led to a severe and significant depletion in haemolymph [Na(+)] and [Cl(-)] compared to organisms exposed in circumneutral water (pH7.3). However, after only a 12h-period of transfer back in neutral water and whatever the previous exposure time (24, 48 and 72h) in both slightly and strongly acidic water, haemolymph [Na(+)] and [Cl(-)] were equal or superior to the control level without associated mortality. In spite of this fast physiological recovery capacity, populations of G. fossarum living in streams undergoing episodic acid stresses were drastically affected thus, demonstrating the high acid-sensitivity of this species. We discuss the possible reasons of population regression and the absence of population recovery.     

Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brévilles, France

The objective of this study was to identify the main controls on atrazine leaching through luvisols and calcisols overlying fissured limestone using the dual-permeability model MACRO. The model parameterisation was based on a combination of direct measurements (e.g. hydraulic properties, adsorption and degradation), literature data and calibration against bromide leaching experiments in field plots. A Monte Carlo sensitivity analysis was carried out for a typical application pattern, considering two different depths of unsaturated limestone (15 and 30 m). MACRO calibrations to the field experiments demonstrated the occurrence of strong macropore flow in the luvisol, while transport in the calcisol could be described by the advection-dispersion equation. MACRO simulations of tritium and atrazine leaching qualitatively matched tritium concentration profiles measured in the limestone and atrazine concentrations measured in piezometers and in aquifer discharge via a spring. The sensitivity analysis suggested that the thickness of the limestone, as well as the transport properties and processes occurring in the unsaturated rock (e.g. matrix vs. fissure flow) will have little significant long-term effect on atrazine leaching, mainly because degradation is very slow in the limestone. No mineralization of atrazine was detected in one-year incubations and a mean half-life of 10 years was assumed in the simulations. Instead, processes occurring in the soil exerted the main control on predicted atrazine leaching, especially variations in the degradation rate and the strength of sorption and macropore flow. However, fissure flow in unsaturated rock is expected to exert a much more significant control on groundwater contamination for compounds that degrade more readily in the deep vadose zone.     

Tradescantia micronucleus test indicates genotoxic potential of traffic emissions in European cities

Urban atmospheres contain complex mixtures of air pollutants including mutagenic and carcinogenic substances such as benzene, diesel soot, heavy metals and polycyclic aromatic hydrocarbons. In the frame of a European network for the assessment of air quality by the use of bioindicator plants, the Tradescantia micronucleus (Trad-MCN) test was applied to examine the genotoxicity of urban air pollution. Cuttings of Tradescantia clone #4430 were exposed to ambient air at 65 monitoring sites in 10 conurbations employing a standardised methodology. The tests revealed an elevated genotoxic potential mainly at those urban sites which were exposed to severe car traffic emissions. This bioassay proved to be a suitable tool to detect local 'hot spots' of mutagenic air pollution in urban areas. For its use in routine monitoring programmes, however, further standardisation of cultivation and exposure techniques is recommended in order to reduce the variability of results due to varying environmental conditions.     

Development of the high spatial resolution EMICAT2000 emission model for air pollutants from the north-eastern Iberian Peninsula (Catalonia, Spain)

Ozone (O(3)) pollution episodes take place in Catalonia (NE of the Iberian Peninsula), mainly during summertime. The complex O(3) behaviour could be understood by using a Chemical Transport Model (CTM). Emission inventories provide the spatial and temporal emissions distribution of the O(3) precursors and other pollutants required by this approach. We developed the EMICAT2000 model with high spatial (cells of 1 km(2)) and temporal (1h) resolutions, to estimate the emissions during the year 2000 from Catalonia. Total annual emissions were 107 kt yr(-1) of NO(x), 137 kt yr(-1) of NMVOC, 267 kt yr(-1) of CO, 65 kt yr(-1) of SO(2), 24 kt yr(-1) of TSP and 32,175 kt yr(-1) of equivalent CO(2). Main NO(x) sources are on-road traffic (58%) and industries (38%). Main NMVOC sources are on-road traffic (36%), vegetation (34%) and use of solvents (13%). Speciation was established according to the Carbon Bond IV mechanism. EMICAT2000 generates directly the data files required for the third generation CTM Models-3/CMAQ.