Modelling the extra and intracellular uptake and discharge of heavy metals in Fontinalis antipyretica transplanted along a heavy metal and pH contamination gradient

Samples of the aquatic bryophyte Fontinalis antipyretica Hedw. were transplanted to different sites with the aim of characterizing the kinetics of the uptake and discharge of heavy metals in the extra and intracellular compartments. The accumulation of metals in extracellular compartments, characterized by an initial rapid accumulation, then a gradual slowing down over time, fitted perfectly to a Michaelis-Menten model. The discharge of metals from the same compartment followed an inverse linear model or an inverse Michaelis-Menten model, depending on the metal. In intracellular sites both uptake and discharge occurred more slowly and progressively, following a linear model. We also observed that the acidity of the environment greatly affected metal accumulation in extracellular sites, even when the metals were present at relatively high concentrations, whereas the uptake of metals within cells was much less affected by pH.     

Increased thyroid volume and frequency of thyroid disorders signs in schoolchildren from nitrate polluted area

Thyroid volume (ThV) and echogenicity by ultrasound were estimated in 324 schoolchildren (aged between 10 and 13-years) from high nitrate area (HNA) located in agricultural lowland with high nitrate drinking water supply (51-274 mg/l) from shallow wells. The data were compared to children of the same age from low nitrate area (LNA) consisting of 168 children from the neighboring area with very low nitrate (< 2 mg/l) drinking water and of 596 children from the city of Kosice located in a vicinity of LNA and also supplied by low nitrate water. Blood samples were obtained from 315 willing children from HNA and 109 children from LNA and the levels of thyrotropin (TSH), total thyroxine (TT4), free triiodothyronine (FT3) and thyroperoxidase antibodies (anti-TPO) in serum were determined. ThV (mean +/- SE) in 10-year (5.10 +/- 0.14 ml) and 13-year (5.97 +/- 0.11 ml) old children from HNA was significantly higher than that in two groups of respective age from LNA, 4.58 +/- 0.17 (p < 0.02) and 5.23 +/- 0.15 ml (p < 0.05), and from the city of Kosice, 4.77 +/- 0.10 ml (p < 0.05) and 4.87 +/- 0.1 0ml (p < 0.0001). The frequency of hypoechogenicity in HNA was also significantly higher than that in pooled LNA plus Kosice, 13.7% vs. 4.7% (p < 0.01) in 10-year and 10.6% vs. 5.7% (p < 0.03) in 13-year, respectively. The frequency of TSH level in the range of subclinical hypothyroidism (> 4.0 mU/l) in pooled age groups from HNA was 13/324 (4.0%) and that of positive anti-TPO was 8/324 (2.5%), while no case of either increased TSH or positive anti-TPO was found in 109 children from LNA. Finally, no differences in the levels of TT4 and FT3 were found between HNA and LNA. It was concluded that long-term exposure to high nitrate intake by drinking water and home made meals from local products results in increased thyroid volume and increased frequency of signs of subclinical thyroid disorders (thyroid hypoechogenicity by ultrasound, increased TSH level and positive anti-TPO).     

Decolourization of synthetic dyes by Trametes hirsuta in expanded-bed reactors

The present paper studies the decolourization of different synthetic dyes (Indigo Carmine, Bromophenol Blue, Methyl Orange and Poly R-478) by the white-rot fungus Trametes hirsuta at bioreactor scale under solid-state conditions, operating with ground orange peelings as a support-substrate. Dye decolourization was performed in both batch and continuous mode. Batch cultivation led to high decolourization percentages in a short time (100% for Indigo Carmine in 3h and 85% for Bromophenol Blue in 7 h). As for continuous cultivation, different hydraulic retention times (HRT) were studied (0.8, 1, 1.5 and 3d). The highest decolourization percentages were obtained operating at a HRT of 3d, especially for the dyes Methyl Orange and Poly R-478 (81.4% and 46.9%, respectively). This is a very interesting result, since there are few studies dealing with the continuous decolourization of dyes at bioreactor scale by fungal laccases.     

Modeling lead bioavailability and bioaccumulation by Lumbriculus variegatus using artificial particles. Potential use in chemical remediation processes

Artificial particles, specifically a diverse selection of chromatographical resins, have been recommended and used as a useful experimental model to predict the bioavailability and bioaccumulation of sediment-bound organic chemicals. In this work the same experimental model was adopted to investigate the bioavailability and bioaccumulation of lead by the freshwater oligochaete Lumbriculus variegatus. Particle-water partition coefficients were also determined. Sand particles and the anionic exchange resin promoted a similar uptake and bioaccumulation of lead. Instead, in the presence of the cationic exchanger the metal was not detected in the animals. For neutral particles, the uptake and accumulation depended on the chemistry of the functional groups at the active sites. In addition, a significant negative correlation was found between bioaccumulation and the particle-water partition coefficients. These studies may help to develop alternative methods for chemical remediation of lead-contaminated aquatic systems.     

Contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area, Portugal since the 19th century

The main purpose of this study was to evaluate the contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area (Portugal) since the 19th century. The study was based on pre-industrial and recent data series, the results being analyzed according to the atmospheric chemistry. The treatment of ozone and meteorological data was performed by classical statistics and by time-series analysis. It was concluded that in the 19th century the ozone present in the troposphere was not of photochemical origin, being possible to consider the respective concentrations as reference values. For recent data a cycle of 8h for ozone concentrations could be related to traffic. Compared to the 19th century, the current concentrations were 147% higher (252% higher in May) due to the increased photochemical production associated with the increased anthropogenic emissions.     

Perfluorinated chemicals in selected residents of the American continent

Perfluorinated chemicals (PFCs) are used in multiple consumer products. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the most widely studied PFCs, may be potential developmental, reproductive, and systemic toxicants. Although PFCs seem to be ubiquitous contaminants found both in humans and animals, geographic differences may exist in human exposure patterns to PFCs. We measured 11 PFCs in 23 pooled serum samples collected in the United States from 1990 through 2002, and in serum samples collected in 2003 from 44 residents from Trujillo, Peru. PFOS and PFOA were detected in all the pooled samples; perfluorohexane sulfonic acid (PFHxS) was detected in 21. Median concentrations were 31.1 micrograms per liter (mug/l, PFOS), 11.6 microg/l (PFOA), and 2 microg/l (PFHxS). The 90th percentile concentrations of PFCs in the 44 Peruvian residents were 0.7 microg/l (PFOS), 0.1 microg/l (PFOA), and <0.3 microg/l (PFHxS). The frequencies of detection were 20% (PFOS), 25% (PFOA), and 9% (PFHxS). The frequent detection of selected PFCs in the pooled samples from the United States and the lack of clear concentration trends based on a year of collection suggest a sustained widespread exposure to these compounds among US residents, at least since the 1990s. By contrast, the much lower frequency of detection and concentration ranges of PFCs in Peru suggest a lower exposure of Peruvians to PFCs compared with North Americans. Genetic variability, diet, lifestyle, or a combination of all these may contribute to the different patterns of human exposure to PFCs in the United States and Peru.     

Removal of trichloroethylene from water by cellulose acetate supported bimetallic Ni/Fe nanoparticles

In this study, cellulose acetate (CA) supported Ni/Fe nanoparticles were prepared and the ability of these nanoparticles to remove trichloroethylene (TCE) from water was studied. The effects of TCE reduction by the nanoparticles and sorption by the CA support were accounted for separately in the model. CA supported post-coated Ni/Fe nanoparticles were used to investigate the effect of metal particle composition on the observed reduction rate constant. The results show that the metal mass normalized observed reduction rate constant was proportional to the Ni content in the post-coated Ni/Fe nanoparticles in the range of 0-14.3 wt.%. This constant reached a maximum between 14.3 and 21.4 wt.% and decreased with further increase in Ni content. CA supported co-reduced Ni/Fe bimetallic nanoparticles gave poorer performance compared to CA supported post-coated Ni/Fe bimetallic nanoparticles at the same Ni content in Ni/Fe nanoparticles.     

Eisenia fetida increased removal of polycyclic aromatic hydrocarbons from soil

The removal of phenanthrene, anthracene and benzo(a)pyrene added at three different concentrations was investigated with or without earthworms (Eisenia fetida) within 11 weeks. Average anthracene removal by the autochthonous micro-organisms was 23%, 77% for phenanthrene and 13% for benzo(a)pyrene, while it was 51% for anthracene, 47% for benzo(a)pyrene and 100% for phenanthrene in soil with earthworms. At 50 and 100mg phenanthrene kg(-1)E. fetida survival was 91% and 83%, but at 150 mg kg(-1) all died within 15 days. Survival of E. fetida in soil amended with anthracene < or = 1000 mg kg(-1) and benzo(a)pyrene < or = 150 mg kg(-1) was higher than 80% and without weight loss compared to the untreated soil. Only small amounts of PAHs were detected in the earthworms. It was concluded that E. fetida has the potential to remove large amounts of PAHs from soil, but more work is necessary to elucidate the mechanisms involved.     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

Dip-angle influence on areal DNAPL recovery by co-solvent flooding with and without pre-flooding

A two-dimensional (2D) laboratory model was used to study effects of gravity on areal recovery of a representative dense non-aqueous phase liquid (DNAPL) contaminant by an alcohol pre-flood and co-solvent flood in dipping aquifers. Recent studies have demonstrated that injection of alcohol and co-solvent solutions can be used to reduce in-situ the density of DNAPL globules and displace the contaminant from the source zone. However, contact with aqueous alcohol reduces interfacial tension and causes DNAPL swelling, thus facilitating risk of uncontrolled downward DNAPL migration. The 2D laboratory model was operated with constant background gradient flow and a DNAPL spill was simulated using tetrachloroethene (PCE). The spill was dispersed to a trapped, immobile PCE saturation by a water flood. Areal PCE recovery was studied using a double-triangle well pattern to simulate a remediation scheme consisting of an alcohol pre-flood using aqueous isobutanol ( approximately 10% vol.) followed by a co-solvent flood using a solution of ethylene glycol (65%) and 1-propanol (35%). Experiments were conducted with the 2D model oriented in the horizontal plane and compared to experiments at the 15 degrees and 30 degrees dip-angle orientations. Injection was applied either in the downward or upward direction of flow. Experimental results were compared to theoretical predictions for flood front stability and used to evaluate effects of gravity on areal PCE recovery. Sensitivity experiments were performed to evaluate effects of the alcohol pre-flood on PCE areal recovery. For experiments conducted with the alcohol pre-flood and the 2D model oriented in the horizontal plane, results indicate that 89-93% of source zone PCE was recovered. With injection oriented downward, results indicate that areal PCE recovery was 70-77% for a 15 degrees dip angle and 57-59% for a 30 degrees dip angle. With injection oriented upward, results indicate that areal PCE recovery was 57-60% at the 30 degrees dip angle, which was similar to PCE recovery for injection in the downward flow direction. Lower areal PCE recovery at greater dip angles in either direction of flow was attributed to DNAPL swelling and migration, flood front instabilities and bypassing of the displaced fluid past the extraction wells during the alcohol pre-flood. Additional results demonstrate that the use of an alcohol pre-flood can be beneficial in improving DNAPL recovery in the horizontal orientation, but pre-flooding may reduce areal recovery efficiency in dip-angle orientations. This study also demonstrates the use of theoretical perturbation (fingering) analysis in predicting NAPL recovery efficiency for flooding processes in remediating aquifers with dip angles.