Catalytic upgrading of higher 1-alkenes from polyethylene thermal cracking by modified Wacker oxidation

The economic success of feedstock recycling procedures for plastic wastes is increasingly demanding the conversion of the starting residue into more valuable chemicals. Thermal cracking of polyethylenes leads to the preparation of equimolar mixtures of n-paraffins and 1-alkenes within the C₂–C₁₀₀ range. These 1-olefins can be catalytically upgraded by selective oxidation processes to more valuable products (e.g., ketones and fatty acids) with different uses such as polar waxes, cetane improvers, varnishes, and printer inks. The results obtained on oxidation in a modified Wacker system of a model 1-olefin (1-dodecene) as well as of a distillate cut (C₁₀–C₂₅) of the product from the thermal cracking of urban polyethylene waste are described.     

Interaction of short-term testosterone treatment with osmotic acclimation in the gilthead sea bream <Emphasis Type="Italic">Sparus auratus</Emphasis>

To assess the interaction between testosterone (T) treatment and acclimation to different salinities, seawater-acclimated gilthead sea bream (Sparus auratus) were implanted with slow-release coconut oil implants alone (control) or containing T (5 μg/g body mass). After 5 days, eight fish of control and T-treated groups were sampled. The same day, eight fish of each group were transferred to low salinity water (LSW, 6 ppt, hypoosmotic test), seawater (SW, 38 ppt, control test) and high salinity water (HSW, 55 ppt, hyperosmotic test) and sampled 9 days later. Gill Na⁺, K⁺-ATPase activity increased in HSW-acclimated fish with respect to SW- and LSW-acclimated fish in both control and T-treated groups. Kidney Na⁺, K⁺-ATPase activity was also enhanced in HSW-acclimated fish, but only in T-treated group. From a metabolic point of view, most of the changes observed can be attributed to the action of salinity and T treatment alone, since few interactions between T treatment and osmotic acclimation to different salinities were observed. Those interactions included in treated fish: in the liver, decreased capacity in using glucose in fish acclimated to extreme salinities; in the gills, decreased capacity in using amino acids in HSW; in the kidneys increased capacity in using amino acids in extreme salinities; and in the brain, decreased glycogen and acetoacetate levels of fish in LSW.     

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag–Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag–PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72 h in freshwater (500–600 μg L⁻¹) and seawater (1300–1500 μg L⁻¹), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag⁺ (1.1, 400 and 0.11 μg L⁻¹, respectively), Ag–Cit (3.0, 2380 and 0.15 μg L⁻¹, respectively) and Ag–PVP (19.5, 3690 and 2.0 μg L⁻¹, respectively) varied widely, with toxicity in the order Ag⁺ > Ag–Cit > Ag–PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag⁺ or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Removal of famoxadone, fluquinconazole and trifloxystrobin residues in red wines: effects of clarification and filtration processes

The effects of six clarification agents [egg albumin, blood albumin, bentonite + gelatine, charcoal, polyvinylpolypyrrolidine (PVPP) and silica gel] on the removal of residues of three fungicides (famoxadone, fluquinconazole and trifloxystrobin) applied directly to a racked red wine, elaborated from Monastrell variety grapes from the D.O. Region of Jumilla (Murcia, Spain) were studied. The clarified wines were filtered with 0.45 microm nylon filters to determine the influence of this winemaking process in the disappearance of fungicide residues. Analytical determination of fluquinconazole and trifloxystrobin was performed by gas chromatography with electron captor detector (ECD), while that of famoxadone using an HPLC equipped with a diode array detector (DAD). Generally, trifloxystrobin is the fungicide that is the lowest persistent one in wines, except in the egg albumin study whereas, the most persistent one is fluquinconazole. The elimination depends on the nature of the active ingredient, though the water stability in the presence of light within it has more influence than the solubility and polarity of the product itself. The most effective clarifying agents were the charcoal and PVPP. The silica gel and bentonite plus gelatine were not enough to reduce considerably the residual contents in the wine clarified with them. In general terms, filtration is not an effective step in the elimination of wine residues. The greatest removal after filtration is obtained in wines clarified with egg albumine and bentonite plus gelatine, and the lowest in those clarified with PVPP.     

Biological Adverse Effects on Bivalves Associated with Trace Metals Under Estuarine Environments

Toxic effects of pollutants on marine organisms can be studied both by performing field measurements, and by undertaking laboratory simulation experiments. Here is described the effect of trace metals Zn, Cd, Pb and Cu on the clam Scrobicularia plana along a salinity gradient simulated in a hypothetical estuary using simulation experiments. The simulator produces a continuous entry of trace metals into the estuary through injection in the lower salinity tank of the system. The clams were exposed during two weeks to different concentration of trace metals to assess the bioaccumulation process along a salinity gradient. Bivalves were analysed for body tissue residue to determine the bioaccumulation factors related to each metal and the salinity influence was addressed. Differences among tanks were observed as a result of the salinity gradient. In the achieved assays, the mechanism of bioaccumulation of Zn and Cd in organisms was more efficient at high salinity values. Bioaccumulation factors for both metals showed a linear increase with the increase of salinity values. It seems that the mechanism of bioaccumulation of Pb and Cu in organisms was dependent on two simultaneous processes: the proximity to the input point of metals and the low salinity values.     

Are native naiads more tolerant to pollution than exotic freshwater bivalve species? An hypothesis tested using physiological responses of three species transplanted to mercury contaminated sites in the Ebro River (NE, Spain)

In the lower Ebro River exist the paradoxical convergence of relatively well preserved river dynamics with the historical presence of a chloralkali plant with a long history of mercury discharges and the recent invasion of foreign bivalves species. Here we performed a comparative study on two alien bivalves, the Zebra mussel and the Asian clam (Dreissena polymorpha and Corbicula fluminea), and one protected species of naiads (Psilunio littoralis), which is the most common species of the freshwater mussel assemblages in this river. Individuals of the three species were transplanted to three sites that included a clean unpolluted upstream site, a contaminated location next to the mercury source and a downstream one. The study focused on digestive gland antioxidant and oxidative stress responses such as antioxidant enzymes, glutathione S transferase, glutathione levels, metallothionein proteins, DNA strand breaks and lipid peroxidation levels. Results evidenced interspecies differences on accumulation levels of mercury, antioxidant defensive systems and oxidative tissue damage. The naiad species, despite of accumulating more mercury showed the greatest antioxidant defensive potential, which was characterized by having high constitutive activities of glutathione S transferase and inducible activities and levels of key antioxidant enzymes and glutathione. Exposed individuals of C. fluminea had moderate levels of metal accumulation, the highest activities of antioxidant enzymes but also high levels of lipid peroxidation. D. polymorpha mussels showed the lowest levels of mercury but the lowest antioxidant responses and consequently the highest levels of oxidative injuries in the DNA and of mortality. Our results support the hypothesis that naiad species might be more tolerant to pollution than exotic species.     

Distribution and biological impact of dioxin-like compounds in risk zones along the Ebro River basin (Spain)

The aim of this investigation was to evaluate the environmental impact associated to PCDDs/Fs and dioxin-like PCBs in the Ebro River basin. Sediments and fish from several species were sampled at three sites with different historical pollution records, including the Barbastro area with different industrial activities, and the Flix and Monzón sites, associated to heavy organochlorine compound pollution. Seventeen toxic PCDDs/Fs and 12 dioxin-like PCBs were analyzed by GC-MS. The results obtained indicated significant accumulation of dioxin-like PCBs, but not PCDDs/Fs, in sediments and fish at the Flix site compared to the other sites. Concomitantly, cytochrome p450 1A (CYP1A) expression, a known indicator for pollution by dioxins and dioxin-like PCBs, was significantly elevated in barbel (Barbus graellsii) from the Flix site, compared to the population from the Barbastro site. CYP1A expression correlated with the concentration of dioxin-like PCBs in the fish fat, whereas no significant correlation was found with PCDDs/Fs concentrations. Our data suggest a significant biological impact at the Flix site, closely related to the presence of dioxin-like PCBs, whereas the PCDDs/Fs contribution to this impact appears to be non-significant, at least in the studied sites.     

Human exposure to fluoride from tea (Camellia sinensis) in a volcanic region—Canary Islands,Spain

Fluoride is highly present in the environment, especially in water and its derivatives. Excessive fluoride contribution to diet poses a health risk. Tea leaves accumulate fluoride and the consumption of tea (Camellia sinensis) could pose a risk to human by the excessive fluoride intake. Ninety tea samples were analyzed by potentiometry using a selective fluoride ion electrode. Mixed tea samples (2.82?±?1.11 mg/L) and black tea samples (2.28?±?0.79 mg/L) recorded the highest fluoride levels. The contribution of drinking water is important for increasing fluoride levels in teas. The daily consumption of two cups (250 mL per cup) of mixed and black teas prepared with La Laguna tap water does pose a health risk for children (4–8 years old) because of the high contribution percentages (74.4% and 63.6%, respectively) of the Tolerable Upper Intake Level set in 2.5 mg/day by the EFSA (European Food Safety Authority). A minor consumption in children (4–8 years old) and adults during pregnancy is advisable.