Fate of β-blockers in aquifer material under nitrate reducing conditions: Batch experiments

The fate of the three environmentally relevant β-blockers atenolol, metoprolol and propranolol has been studied in batch experiments involving aquifer material and nitrate reducing conditions. Results from the about 90 d long tests indicate that abiotic processes, most likely sorption, jointly with biotransformation to atenololic acid were responsible for the 65% overall removal observed for atenolol. Zero order kinetics, typical of enzyme-limited reactions, controlled the transformation of this beta blocker to its corresponding carboxylic acid. The mass balance evidences that no mineralization of atenolol occurs in the biotic experiment and that atenololic acid is more stable than its parent compound under the studied conditions. This finding stresses the importance of considering atenololic acid as target compound in the environmental studies on the fate of atenolol. For metoprolol and propranolol the results from the experiment suggest a slower sorption to be the dominant removal process, which led to final decreases in concentrations of 25-30% and 40-45%, respectively. Overall, the removals observed in the experiments suggest that subsurface processes potentially constitute an alternative water treatment for the target beta-blockers, when compared to the removals reported for conventional wastewater treatment plants.     

Characterization of atmospheric aerosols by SEM in a rural area in the western part of México and its relation with different pollution sources

Samples of particulate matter were collected during the period from October 2006 through September 2007 in a rural station located 12 km from the city of Colima. A total of 3600 particles were analyzed by SEM-EDS and then classified by their chemical composition and morphology in order of abundance: those rich in C, Fe, Si–Al, Cl–Na, Ca, Ba; and to a lesser abundance, particles rich in heavy metals such as Pb and V–Ni were observed. A factorial analysis was carried out to determine the main elements related with the emission sources such as crustal/farming; fuel-oil; marine; volcanic activity and industry. Trough the seasons, the dominant winds causes the presence of anthropogenic particles in the rural site. The information presented in this study aims to give insight and detailed of the analysis of the morphological characteristics and chemical composition of atmospheric particles at individual level in a rural site from Colima State, Mexico.     

Analysis of micronucleated erythrocytes in heron nestlings from reference and impacted sites in the Ebro basin (N.E. Spain)

The frequency of micronuclei (MN) in peripheral erythrocytes was tested for 59 heron nestlings (Ardea purpurea, Egretta garzetta and Bubulcus ibis) sampled at two areas (polluted and reference) on the River Ebro (NE Spain) and at its Delta during Spring 2006. Flow-cytometry analysis revealed higher (three- to six-fold) MN counts in samples from the most polluted site relative to samples from the reference area. Samples from the Delta showed intermediate values. Age, morphometric parameters (weight, tarsus size and bill-head length) and maturation status showed no significant differences among the different populations for each species; nor were they correlated with MN levels. The data suggest that elevated levels of MN in chicks in impacted areas reflected the chemical pollution of their nesting sites. The use of nestlings for this assay appears to be a convenient, non-destructive method to assess the impact of pollution in natural bird populations.     

Mechanistics of trichloroethylene mineralization by the white-rot fungus Trametes versicolor

The white-rot fungus Trametes versicolor degraded trichloroethylene (TCE), a highly oxidized chloroethene, and produced 2,2,2-trichloroethanol and carbon dioxide as the main products of degradation, based on the results obtained using [13C]-TCE as the substrate. For a range of concentrations of TCE between 2 and 20 mg l(-1), 53% of the theoretical maximum chloride expected from complete degradation of TCE was observed. Laccase was shown to be induced by TCE, but did not appear to play a role in TCE degradation. Cytochrome P-450 appears to be involved in TCE degradation, as evidenced by marked inhibition of degradation of TCE in the presence of 1-aminobenzotriazole, a known inhibitor of cytochrome P-450. Our results suggested that chloral (trichloroacetaldehyde) was an intermediate of the TCE degradation pathway. The results indicate that the TCE degradation pathway in T. versicolor appears to be similar to that previously reported in mammals and is mechanistically quite different from bacterial TCE degradation.     

Persistence and effect of processing on reduction of fipronil and its metabolites in chilli pepper (Capsicum annum L.) fruits

A single laboratory UPLC-MS/MS method was developed and validated for the estimation of fipronil and its metabolites in fresh and dry chilli pepper fruits. Dissipation of fipronil on chilli fruits was studied following the application of fipronil (Jump 80 WG) at 40 and 80 g active ingredient (a.i.) ha^?1 in the fruiting stage of the crop. The initial deposits of total fipronil on fresh chilli fruits at single and double dose application were 0.69 and 1.43 μg g^?1, respectively, and were dissipated to below quantitation level at 27 days after application. The half-life of fipronil at single and double dose in fresh chilli pepper was 4.22 and 4.32 days and the waiting period was 25.9 and 30.6 days, respectively. Processing factor due to sun drying was calculated by measuring fipronil residues in dry chilli fruits, and it ranged from 2.96 to 3.50 during 0 to 21st day after application. Among the metabolites of fipronil, fipronil desulfenyl and fipronil sulfone had maximum residues in fresh and dried chilli, respectively, followed by fipronil sulfide. Dipping in solutions of tamarind, turmeric, vinegar and slaked lime and wet scrubbing could remove more than 90 % of fipronil residues in fruits.     

Chronic dietary exposure to pyrolytic and petrogenic mixtures of PAHs causes physiological disruption in zebrafish—part II: behavior

In the last 10 years, behavior assessment has been developed as an indicator of neurotoxicity and an integrated indicator of physiological disruption. Polycyclic aromatic hydrocarbon (PAH) release into the environment has increased in recent decades resulting in high concentrations of these compounds in the sediment of contaminated areas. We evaluated the behavioral consequences of long-term chronic exposure to PAHs, by exposing zebrafish to diets spiked with three PAH fractions at environmentally relevant concentrations. Fish were exposed to these chemicals from their first meal (5 days postfertilization) until they became reproducing adults (at 6 months old). The fractions used were representative of PAHs of pyrolytic (PY) origin and of two oils differing in composition (a heavy fuel oil (HO) and a light crude oil (LO)). Several tests were carried out to evaluate circadian spontaneous swimming activity, responses to a challenge (photomotor response), exploratory tendencies, and anxiety levels. We found that dietary PAH exposure was associated with greater mobility, lower levels of exploratory activity, and higher levels of anxiety, particularly in fish exposed to the HO fraction and, to a lesser extent, the LO fraction. Finally, our results indicate that PAH mixtures of different compositions, representative of situations encountered in the wild, can induce behavioral disruptions resulting in poorer fish performance.     

Developmental toxicity of PAH mixtures in fish early life stages. Part I: adverse effects in rainbow trout

A new gravel-contact assay using rainbow trout, Oncorhynchus mykiss, embryos was developed to assess the toxicity of polycyclic aromatic hydrocarbons (PAHs) and other hydrophobic compounds. Environmentally realistic exposure conditions were mimicked with a direct exposure of eyed rainbow trout embryos incubated onto chemical-spiked gravels until hatching at 10 °C. Several endpoints were recorded including survival, hatching delay, hatching success, biometry, developmental abnormalities, and DNA damage (comet and micronucleus assays). This bioassay was firstly tested with two model PAHs, fluoranthene and benzo[a]pyrene. Then, the method was applied to compare the toxicity of three PAH complex mixtures characterized by different PAH compositions: a pyrolytic extract from a PAH-contaminated sediment (Seine estuary, France) and two petrogenic extracts from Arabian Light and Erika oils, at two environmental concentrations, 3 and 10 μg g^?1 sum of PAHs. The degree and spectrum of toxicity were different according to the extract considered. Acute effects including embryo mortality and decreased hatching success were observed only for Erika oil extract. Arabian Light and pyrolytic extracts induced mainly sublethal effects including reduced larvae size and hemorrhages. Arabian Light and Erika extracts both induced repairable DNA damage as revealed by the comet assay versus the micronucleus assay. The concentration and proportion of methylphenanthrenes and methylanthracenes appeared to drive the toxicity of the three PAH fractions tested, featuring a toxic gradient as follows: pyrolytic?Arabian Light?Erika. The minimal concentration causing developmental defects was as low as 0.7 μg g^?1 sum of PAHs, indicating the high sensitivity of the assay and validating its use for toxicity assessment of particle-bound pollutants.     

Inhibition equivalency factors for microcystin variants in recombinant and wild-type protein phosphatase 1 and 2A assays

In this work, protein phosphatase inhibition assays (PPIAs) have been used to evaluate the performance of recombinant PP1 and recombinant and wild-type PP2As. The enzymes have been compared using microcystins-LR (MC-LR) as a model cyanotoxin. Whereas PP2A_Rec provides a limit of detection (LOD) of 3.1 μg/L, PP1_Rec and PP2A_Wild provide LODs of 0.6 and 0.5 μg/L, respectively, lower than the guideline value proposed by the World Health Organization (1 μg/L). The inhibitory potencies of seven MC variants (-LR, -RR, -dmLR, -YR, -LY, -LW and -LF) have been evaluated, resulting on 50 % inhibition coefficient (IC₅₀) values ranging from 1.4 to 359.3 μg/L depending on the MC variant and the PP. The PPIAs have been applied to the determination of MC equivalent contents in a natural cyanobacterial bloom and an artificially contaminated sample, with multi-MC profiles. The inhibition equivalency factors (IEFs) have been applied to the individual MC quantifications determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, and the estimated MC-LR equivalent content has been compared to PPIA results. PPIAs have demonstrated to be applicable as MC screening tools for environmental applications and to protect human and animal health.