Fast and complete removal of the 5-fluorouracil drug from water by electro-Fenton oxidation

Cytostatic drugs are a troublesome class of emerging pollutants in water owing to their potential effects on DNA. Here we studied the removal of 5-fluorouracil from water using the electro-Fenton process. Galvanostatic electrolyses were performed with an undivided laboratory-scale cell equipped with a boron-doped diamond anode and a carbon felt cathode. Results show that the fastest degradation and almost complete mineralization was obtained at a Fe²⁺ catalyst concentration of 0.2 mM. The absolute rate constant for oxidation of 5-fluorouracil by hydroxyl radicals was 1.52 × 10⁹ M^?1 s^?1. Oxalic and acetic acids were initially formed as main short-chain aliphatic by-products, then were completely degraded. After 6 h the final solution mainly contained inorganic ions (NH₄ ⁺, NO₃ ^? and F^?) and less than 10% of residual organic carbon. Hence, electro-Fenton constitutes an interesting alternative to degrade biorefractory drugs.     

Nanosystems for drug delivery of coenzyme Q10

Coenzyme Q10 is an antioxidant present in the human body. Coenzyme Q10 has an essential role in various biochemical reactions. The deficiency of coenzyme Q10 in the body leads to disorders including neurological degeneration, ageing and cancer. Clinical trials have tested coenzyme Q10 as a drug or a dietary supplement. However, the major pharmaceutical issue of coenzyme Q10 delivery is its high molecular weight and poor water solubility. This limitation leads to its poor oral bioavailability. Several methods have been designed to overcome the poor water solubility of coenzyme Q10, such as size reduction and ionization. This article presents nanotechnology-based drug delivery systems for coenzyme Q10 with special emphasis on pharmacokinetic perspectives and clinical relevance. Systems include nanoparticles, solid dispersions, liposomes, nanoemulsions, self-emulsifying drug delivery systems, nanostructured lipid carriers, cyclodextrins and nanocapsules.     

Nanoscience in food and agriculture: research,industries and patents

High population rise and climate changes are increasing issues of agricultural production and food safety. Nanotechnology is finding revolutionary applications to improve agricultural and food systems, notably for better crop production and food preservation. Here we review research, industrial and patent trends of nanoscience in food and agriculture. In a literature survey, we found 44.6% publications in the nano-food research area during the years 2013–2015 and 59.09% publications in the nano-agriculture research area during 2012–2015. USA is leading in the development of nanotechnology firms with a maximum share of 75.5% of the total firms, followed by Germany and France with 8.10 and 4.74%, respectively. USA is leading in the nano-food research with 22 granted patents, whereas China is placed first in nano-agriculture research with 28 granted patents during assessment years 2011–2015. Nano-food research focused mainly on nano-food packaging with 76.84% contributions, whereas in nano-agriculture research, focus has been on nano-fertilizers with 90% contributions. Germany, France, Korea, Italy, Czech Republic, Slovenia and Slovak republic have more than 20% of dedicated nanotechnology firms. A growth of about 45% in nano-food patents has been observed for USA during 2011–2015, and China is leading in the nano-agriculture patents with an increase of 60.7% during 2012–2015.     

High zinc removal from water and soil using struvite-supported diatomite obtained by nitrogen and phosphate recovery from wastewater

Zinc is known as an essential element of human life. However, excessive zinc discharge into water and soil causes water pollution, leading to serious health issues such as septicemia, meningitis and iron-deficiency anemia. Here, a novel material made of struvite-supported diatomite was obtained from eutrophic water treated by mesoporous MgO-modified diatomite. This material was applied for zinc remediation in aqueous solutions and contaminated soils to test the reuse of P-containing products. Struvite-supported diatomite was characterized by field emission scanning electron microscopy and X-ray diffraction. Results show that the maximum removal efficiency of Zn(II) from wastewater streams reached 90.54% at an initial pH of 5 and struvite-supported diatomite dosage of 0.3 g/L. Moreover, the X-ray diffraction patterns of precipitates after Zn(II) sorption show that the combination between zinc and the phosphate group played a key role for zinc removal in solution. For Zn-contaminated soils amended with 10% struvite-supported diatomite, available Zn decreased by 65.38% and acid soluble Zn decreased by 56.9% after 56 days.     

High CO<Subscript>2</Subscript> adsorption by amino-modified bio-spherical cellulose nanofibres aerogels

Climate change has become increasingly serious due to the greenhouse effect. It is therefore necessary to control the content of greenhouse gases such as carbon dioxide in the atmosphere, using, for instance, CO₂-adsorbing materials. Here, we synthesized ultra-lightweight and spherical cellulose nanofibres aerogels by a suspension titration method using an efficient amination process. These functional materials with high porosity, higher than 96.54%, and three-dimensional network structure, were prepared by freeze-drying spherical cellulose nanofibres hydrogel. Their maximum CO₂ adsorption capacity reaches 1.78 mmol/g, and they show excellent regeneration, of more than 10 cycles. This synthesis of bioaerogels represents a new method for the preparation of bio-CO₂ adsorbents.     

Free radical-assisted electrocoagulation processes for wastewater treatment

The combination of electrocoagulation with another process is a promising approach to enhance the removal efficiency of water pollutants. For instance, free radical-assisted electrocoagulation is a new combination showing higher performance. There are different combinations depending on the free radical source. This article reviews free radical-assisted electrocoagulation processes. We discuss electrocoagulation mechanisms; ozone-assisted electrocoagulation processes; advanced oxidation-assisted electrocoagulation processes; and ultrasound-assisted electrocoagulation. We present kinetic models used in free radical-assisted electrocoagulation, scale-up of free radical-assisted electrocoagulation and cost estimation. The major points are: most of the available studies have been done at laboratory scale with synthetic wastewater, and lack holistic and systematic approaches to consider the process complexity. The performance of the combined process is improved, and the removal efficiency is increased especially with ozone-assisted electrocoagulation, which gives a removal efficiency of more than 95%. The use of ultrasound energy with electrocoagulation is advantageous in reducing the problem of electrode passivation.     

Effect of herbicides on glutathione S-transferases in the earthworm, <Emphasis Type="Italic">Eisenia fetida</Emphasis>

AIM AND BACKGROUND: Earthworms have been studied as a readily available, easily maintainable and cheap test species for assessing chemical pollution, and may be an alternative to in vivo rodent bioassays. The current investigation aims to characterize detoxification enzymes in Eisenia fetida and stress response against two herbicides with different modes of action, namely, fenoxaprop and metolachlor. METHODS: Herbicides were applied to soil containing earthworms. Animals were then collected, sacrificed and shock-frozen. Extracted protein was analyzed for glutathione S-transferase (GST) activity using CDNB (1-chloro-2,4-dinitrobenzene), DCNB (1,2-dichloro-4-nitrobenzene), pNBC (p-nitrobenzylchloride), PNOBC (p-nitrobenz-o-ylchloride) and selected herbicides. GST isoenzymes were partially purified by affinity chromatography and molecular weights were estimated by SDS-PAGE. RESULTS: In E. fetida protein extracts, GST activity towards model compounds ranked as CDNB>DCNB>PNBOC>PNBC. Fluorodifen was not conjugated at all, but fenoxaprop and metolachlor were conjugated at low rates. Furthermore, the GST isoenzyme pattern changed during the incubation with herbicides, either due to stress or as a defense reaction. After incubation with monochlorobimane, a strong fluorescence of the intestinal tract and the intersegments was observed, indicating organ-specific GST induction. DISCUSSION: According to the author's knowledge, here, for the first time, evidence is presented that E. fetida GST are also capable of conjugating a wider range of xenobiotic substrates. Different forms of GST were observed and changes in GST isoforms due to the herbicide treatment were also noticed. GST conjugation rates varied between different herbicides used in this experiment. It might be assumed that herbicides may well be detoxified by earthworms, to a certain extent, but that they are also potent stress factors influencing the detoxification system of the animal. High doses or long exposure might lead to deleterious effects on earthworms and limit their survival rate. The use of the animals as bioindicators for herbicides and herbicide residues seems very promising, but is surely influenced by the lack of detoxification for some compounds. CONCLUSIONS: Conjugation of several xenobiotics with model substances and herbicides is proven in the earthworm E. fetida. However, E. fetida has only limited capabilities of detoxifying herbicidal compounds. Different isoforms of GST were involved and altered in their activity after treatment. RECOMMENDATIONS AND PERSPECTIVES: The accumulation of GS-conjugates and their determination via fluorescence microscopy is a quick and secure, additional marker for exposure that should be further developed to complement existing biotests. The described methods and endpoints might help to understand the complex reaction of earthworms towards herbicides and lead to an adapted test methodology.     

Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.     

Acute toxic hazard evaluations of glyphosate herbicide on terrestrial vertebrates of the oregon coast range

GOAL, SCOPE AND BACKGROUND: The degree to which dose responses of model organisms (lab rodents) can adequately predict dose responses of free-ranging wild mammals or amphibians is unknown, and the relative sensitivity of such species to body loading of a toxicant such as glyphosate is seldom reported. For relative effects of dosage, we compare sensitivity of nine wild vertebrate species to effects of high doses of glyphosate in Swiss-Webster laboratory mice both by gavage and by intraperitoneal injection. We also evaluate sublethal effects of herbicide exposure on behavior and reproductive success of one mammal and one amphibian species. METHODS: Comparisons of acute toxicity of glyphosate were made with intraperitoneal dosings of technical glyphosate isopropylamine salt to nine species of terrestrial vertebrates (five amphibians, four mammals) and compared with responses in Swiss-Webster laboratory mice. Animals collected from sites that had no recent herbicide application were allowed 7-14 days to equilibrate in captivity before treatment. RESULTS: Median lethal dose ranged from 800 to 1,340 mg kg(-1) in mammals, and 1,170 to >2,000 mg kg(-1) in amphibians, with Oregon vole being the most sensitive. White lab mice were in the middle of the mammalian range. Tailed frog, at >2,000 mg kg(-1) was the least sensitive. Calibration of IP sensitivity to oral administration by gavage indicated that roughly four times as much glyphosate must be administered to obtain a comparable estimate of lethality. Administration by gavage in highly concentrated solutions tended to cause physical injury, hence may prove less useful as a relative indicator of toxicity. When sublethal dosages were given to roughskin newts or chipmunks, mobility and use of cover appeared largely unaffected. DISCUSSION: Direct toxic effects of spraying glyphosate under normal forest management seem unlikely for the nine species examined. Nor could we detect significant indirect effects of exposure on behavior and use of cover features in two species. There may be effects on other aspects of the field biology of these animals, such as reproductive rates, which we did not investigate. Recent field data indicate that changes in habitat quality following herbicide application can result in high reproductive activity in species associated with the grasses and forbs that proliferate following field applications. CONCLUSIONS: When compared to field data on body burdens of wild mammals exposed after aerial application of glyphosate at maximum rates in forests, there seems to be a large margin of safety between dosages encountered and those causing either death or limitation of movement, foraging or shelter. RECOMMENDATIONS AND PERSPECTIVES: Margins of safety for small mammals and amphibians appear to be large under any probable exposure scenarios, however our results indicate high variability in responses among species. Uncertainty introduced into field studies from unknown sources of mortality (e.g, likely predation) must be considered when interpreting our results.