Effect of aging on catalytic properties in mechanochemical degradation of pentachlorophenol by birnessite

Mechanochemistry, a technique concerning with milling contaminated samples for prolonged times, induces massive degradation of pollutants by grinding them in ball mills with different soil components or additives. In the present study, laboratory experiments were conducted to evaluate the effect of aging on the mechanochemical efficiency of the Mn-oxide birnessite in degrading pentachlorophenol (PCP). A comparative study on an aged birnessite (KBiA), used after 3 years from synthesis, and a fresh birnessite (KBiF), employed immediately after synthesis, was carried out. The differences between the two birnessites, evidenced by spectroscopic and diffractometric techniques, are mainly relative to reduction of the Mn(IV) centered at the MnO₆ octahedra layers from the birnessite structure, which represent the most reactive sites for PCP degradation. The long term air drying at room temperature, by favouring reduction of Mn(IV) to Mn(III), produces an inorganic substrate that offers paucity of the less reactive sites for PCP degradation, thus reducing the oxidative potential of the KBiA. Accordingly, the more reactive fresh birnessite was employed in the experiment with a polluted soil. Adding a small amount of KBiF to soil only induces a light increase in PCP removal, probably due to the mechanically induced PCP adsorption and transformation onto clay minerals present in the soil. Besides, adding a higher dose of birnessite causes a stronger degradation of PCP.     

Phytoremediation of 2,4-dichlorophenol using wild type and transgenic tobacco plants

Introduction

Transgenic plant strategies based on peroxidase expression or overexpression would be useful for phenolic compound removal since these enzymes play an important role in phenolic polymerizing reactions.

Material and methods

Thus, double transgenic (DT) plants for basic peroxidases were obtained and characterized in order to compare the tolerance and efficiency for 2,4-dichlorophenol (2,4-DCP) removal with WT and simple transgenic plants expressing TPX1 or TPX2 gene. Several DT plants showed the expression of both transgenes and proteins, as well as increased peroxidase activity.

Results

DT lines showed higher tolerance to 2,4-DCP at early stage of development since their germination index was higher than that of WT seedlings exposed to 25?mg/L of the pollutant. High 2,4-DCP removal efficiencies were found for WT tobacco plants. TPX1 transgenic plants and DT (line d) reached slightly higher removal efficiencies for 10?mg/L of 2,4-DCP than WT plants, while DT plants (line A) showed the highest removal efficiencies (98%). These plants showed an increase of 21% and 14% in 2,4-DCP removal efficiency for solutions containing 10 and 25?mg/L 2,4-DCP, respectively, compared with WT plants. In addition, an almost complete toxicity reduction of postremoval solutions using WT and DT plants was obtained through AMPHITOX test, which indicates that the 2,4-DCP degradation products would be similar for both plants.

Conclusion

These results are relevant in the field of phytoremediation application and, moreover, they highlight the safety of using DT tobacco plants because nontoxic products were formed after an efficient 2,4-DCP removal.     

Perfluorinated alkylated substances in vegetables collected in four European countries; occurrence and human exposure estimations

The human diet is recognised as one possible major exposure route to the overall perfluorinated alkylated substances (PFAS) burden of the human population, resulting directly from contamination of dietary food items, as well as migration of PFAS from food packaging or cookware. Most European countries carry out national monitoring programs (food basket studies) to monitor contamination with pollutants. Usually, for PFASs, non-coordinated approaches are used in Europe, since food basket studies are mainly carried out by national authorities following national requirements and questions, making comparisons between different countries difficult. A harmonised sampling campaign collecting similar food items in a uniform procedure enabling direct comparison between different regions in Europe was designed. We selected four countries (Belgium, Czech Republic, Italy and Norway), representing the four regions of Europe: West, East, South and North. In spring 2010 and 2011, 20 different types of vegetables were sampled in Belgium, Czech Republic, Italy and Norway. Perfluorinated carboxylic acids (PFCAs) were the main group of detected PFASs, with perfluorinated octanoic acid (PFOA) as the most abundant PFCA (with exception of samples from Czech Republic), followed by perfluorinated hexanoic acid and perfluorinated nonanoic acid. Dietary intake estimates for PFOA show only low human exposure due to vegetable consumption for adults and children, mostly governed by high intake of potatoes.     

Recent evolution of the physical–chemical characteristics of a Site of National Interest—the Mar Piccolo of Taranto (Ionian Sea)—and changes over the last 20 years

The Mar Piccolo of Taranto, classified as a ‘Site of National Interest’ (SIN), is a semi-enclosed basin divided into two inlets with lagoon features and sea influences, seriously affected by anthropic activities. In the framework of the RITMARE project, a study has been carried out to evaluate the functionality of this ecosystem. As part of this work, measurements of the water abiotic parameters were performed in order to assess the physical–chemical features of this area after the activation, in the last decade, of treatment plants for various urban and industrial dumping. Seawater intrusions and continental inputs, as well as several submarine freshwater springs, clearly affect physical–chemical characteristics of the water column in the two inlets. This finding suggests that small-scale patterns in water circulation have the potential to influence the chemical properties of the seawater. The comparison with a 20-year dataset reveals a drastic decrease in nutrient concentrations after the year 2000, validating the functionality of the treatment plants. The reduction of nutrient inputs into the basin (up to ?90 % in the first inlet characterized by lower hydraulic residence time) has changed the biogeochemical characteristics of the Mar Piccolo from being relatively eutrophic to moderately oligotrophic.     

Degradation of lidocaine,tramadol, venlafaxine and the metabolites O-desmethyltramadol and O-desmethylvenlafaxine in surface waters

The photodegradation and biotic transformation of the pharmaceuticals lidocaine (LDC), tramadol (TRA) and venlafaxine (VEN), and of the metabolites O-desmethyltramadol (ODT) and O-desmethylvenlafaxine (ODV) in the aquatic environmental have been investigated. Photodegradation experiments were carried out using a medium pressure Hg lamp (laboratory experiments) and natural sunlight (field experiments). Degradation of the target compounds followed a first-order kinetic model. Rates of direct photodegradation (light absorption by the compounds itself) at pH 6.9 were very low for all of the target analytes (?0.0059 h^?1 using a Hg lamp and ?0.0027 h^?1 using natural sunlight), while rates of indirect photodegradation (degradation of the compounds through photosensitizers) in river water at pH 7.5 were approximately 59 (LDC), 5 (TRA), 8 (VEN), 15 (ODT) and 13 times (ODV) higher than the rates obtained from the experiments in ultrapure water. The accelerated photodegradation of the target compounds in natural water is attributed mainly to the formation of hydroxyl radicals through photochemical reactions. Biotic (microbial) degradation of the target compounds in surface water has been shown to occur at very low rates (?0.00029 h^?1). The half-life times determined from the field experiments were 31 (LDC), 73 (TRA), 51 (VEN), 21 (ODT) and 18 h (ODV) considering all possible mechanisms of degradation for the target compounds in river water (direct photodegradation, indirect photodegradation and biotic degradation).     

Multiparametric approach for an exemplary study of laser printer emissions

The aim of this work was the study, by a multiparametric approach, of emissions from a laser printer in an experimental box-chamber, with particular attention to nanoparticles release. The experimental design included number concentration measurements by Fast Mobility Particle Sizer (FMPS) and chemical characterizations (elements) of size segregated samples collected by Nanomoudi cascade impactor. Volatile Organic Compounds (VOCs) were also sampled by charcoal sorbent tubes by personal sampling pumps. Monitoring of ozone, total volatile organic compounds concentrations and of temperature and humidity values inside the experimental box during the printing processes were also performed by automatic analyzers. The performed monitoring allowed to evidence different ways for particles emissions by laser printers, in particular showing that nanoparticles, characterised by high concentrations of Ba, Zn, B, K, Sr and Na, are set free at the beginning of the printing process. This emission seems to be directly ascribable to the use of toner powder, as all these elements are present in it. The emission of larger particles (ca. 100-320 nm) was observed in subsequent phases of the print process, probably due to the condensation of vapours released during the progressive heating of the fuser roller. This contribution was proved by both the FMPS measurements and the cascade impactor results. Also, a low emission of particles in higher size ranges was evidenced, mainly due to paper related particles. A very high concentration of VOCs was detected inside the chamber and the chemical speciation shows that the major contribution is associated to toner components, even if some species are released from other printer components. Although the formation of secondary species by reaction of VOCs with ozone cannot be excluded, these species were present inside the chamber at concentrations lower than the detection limit.     

A novel survey of raptor collections in Europe and their potential to provide samples for pan-European contaminant monitoring

Environmental Science and Pollution Research - This paper provides a novel survey of current collections of frozen raptor carcasses and tissue samples in natural history museums (NHMs),...     

River Channel Geometry and Rating Curve Estimation Using Height above the Nearest Drainage

River channel geometry is an important input to hydraulic and hydrologic models. Traditional approaches to quantify river geometry have involved surveyed river cross sections, which cannot be extended to ungaged basins. In this paper, we describe a method for developing a synthetic rating curve to relate flow to water level in a stream reach based on reach‐averaged channel geometry properties developed using the Height above Nearest Drainage (HAND) method. HAND uses a digital elevation model (DEM) of the terrain and computes the elevation difference between each land surface cell and the stream bed cell to which it drains. Taking increments in water level in the stream, HAND defines the inundation zone and a water depth grid within this zone, and the channel characteristics are defined from this water depth grid. We apply our method to the Blanco River (Texas) and the Tar River (North Carolina) using 10‐m terrain data from the United States Geological Survey (USGS) 3D Elevation Program (3DEP) dataset. We evaluate the method's performance by comparing the reach‐average stage‐river geometry relationships and rating curves to those from calibrated Hydrologic Engineering Center's River Analysis System (HEC‐RAS) models and USGS gage observations. The results demonstrate that after some adjustment, the river geometry information and rating curves derived from HAND using national‐coverage datasets are comparable to those obtained from hydraulic models or gage measurements. We evaluate the inundation extent and show our approach is able to capture the majority of the Federal Emergency Management Agency (FEMA) 100‐year floodplain.     

Bioaccessibility of metals in soils: comparison between chemical extractions and in vitro tests

It is well-known that the total metal content in soils is not a good indicator of their harmful effects, leading to an overestimation of risks. Toxicological and environmental hazards depend on the chemical species and on its bioavailability to target organisms. Because a good estimation of bioavailability is difficult, a good compromise is to assess bioaccessibility, defined as the maximum amount of a pollutant which is potentially absorbable by a target organism. This study presents a comparison of different strategies to measure metal bioaccessibility in soils. Three procedures were applied to real soil samples with different levels of metal contamination: pseudo-total metal attack, selective sequential extractions and in vitro tests (deliberately developed to simulate human or mammals digestion). Considering the first step of the selective extraction procedure, which can provide the bioaccessible fraction for deposit-feeder organisms, data obtained for each metal were lower than those obtained from in vitro tests. Therefore, it is possible to highlight that this extraction tends to underestimate metal bioaccessibility in soils for humans, while in vitro tests certainly will overestimate bioaccessibility for organisms as invertebrates. If the sum of first and second step of sequential procedure is considered, results are quite similar to those obtained from in vitro tests, but this kind of procedure would require two days of work rather than a few hours required to perform an in vitro test. Results highlight the diversity among the differently defined bioaccessible fractions and the need to apply the most suitable procedure depending on the target organism.     

Topological analysis of the ecological importance of elasmobranch fishes: A food web study on the Gulf of Tortugas, Colombia

We built a trophic network based on a matrix of interspecific trophic relationships to assess the role of elasmobranch fishes in shaping community structure of the Gulf of Tortugas in the Colombian Pacific Ocean. We analyzed diet similarities to define trophic components (nodes) - rather than taxonomical groups - in the network. We evaluated the ecological function of species or trophic entities through topological analysis of their structural importance in trophic networks by applying one local and several mesoscale network indices. We found that top predatory elasmobranchs play an important ecological role in top-down control and in propagating indirect effects through the system owing to high values of the node degree, centrality and topological importance indices. However, invertebrates and teleost fishes had higher connectivity and topological importance than other elasmobranchs in the network before and after removal of top predators from the system. Results from our study thus suggest that elasmobranchs at intermediate trophic levels - commonly referred to as “mesopredators” - are not so important in all complex coastal ecosystems as previously reported.