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.     

Fate of imidacloprid in soil and plant after application to cotton seeds

This study aimed to investigate the persistence of imidacloprid in soil after application to cotton seeds and to obtain a complete picture on the mass balance of this compound in soil and cotton plants. The study was carried out as a pot culture experiment under laboratory conditions using a Gaucho formulation containing ¹⁴C-labeled imidacloprid. Three treatments of cotton seeds were made in sandy loamy soil: live seeds grown in autoclaved soil, dead seeds put in live soil and live seeds grown in live soil. Results showed that total ¹⁴C recoveries decreased by time ranging 93.8–96.2, 77.1–88.4 and 53.5–62.4% of the applied radioactivity at 7, 14, and 21 d after application, respectively. The reduction in the extracted ¹⁴C from soil coincided with the increase of non-extracted ones. Levels of bound ¹⁴C was always less in autoclaved soil than in live ones. Results revealed also that only 1.8–6.8% of the applied ¹⁴C was taken up by the plants and fluctuated within the test period. ¹⁴C levels were higher in plants grown in autoclaved soil than those in live ones and the radioactivity tended to accumulate on the edges of cotton leaves. Most of the radioactivity in the soil extracts was identified as unchanged ¹⁴C-imidacloprid.     

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.     

Heavy metals effects on proteolytic system in sunflower leaves

Plant proteolytic system includes proteases, mainly localized inside the organelles, and the ubiquitin-proteasome pathway in both, the cytoplasm and the nucleus. It was recently demonstrated that under severe Cd stress sunflower (Helianthus annuus L.) proteasome activity is reduced and this results in accumulation of oxidized proteins. In order to test if under other heavy metal stresses sunflower proteolytic system undergoes similar changes, an hydroponic experiment was carried out. Ten days old sunflower plants were transferred to hydroponic culture solutions devoid (control) or containing 100 microM of AlCl(3), CoCl(2), CuCl(2), CrCl(3), HgCl(2), NiCl(2), PbCl(2) or ZnCl(2) and analyzed for protein oxidative damage and proteolytic activities. After 4 days of metal treatment, only Co(2+), Cu(2+), Hg(2+), and Ni(2+) were found to increase carbonyl groups content. Except for Al(3+) and Zn(2+), all metals tested significantly reduced all proteasome activities (chymotrypsin-like, trypsin-like and PGPH) and acid and neutral proteases activities. The effect on basic proteases was more variable. Abundance of 20S protein after metal treatments was similar to that obtained for control samples. Co(2+), Cu(2+), Hg(2+), Ni(2+), Cr(3+), and Pb(2+) induced accumulation of ubiquitin conjugated proteins. It is concluded that heavy metal effects on proteolytic system cannot be generalized; however, impairment of proteasome functionality and decreased proteases activities seem to be a common feature involved in metal toxicity to plants.     

Implications of urine-to-feces ratio in the thermophilic anaerobic digestion of swine waste.

Thermophilic anaerobic digestion of swine manure represents a potential waste treatment technology to address environmental concerns, such as odor emissions and removal of pathogenic microorganisms. However, there are concerns relative to the stability of this process when swine manure is the sole substrate. In this study, the potential of biogas production from swine manure as the sole substrate under thermophilic (50 degrees C) conditions was investigated in the laboratory, to determine whether separation of urine and feces as part of the waste collection process would benefit anaerobic digestion. Effluent from a continuously stirred tank reactor was used as the inoculum for batch tests, in which the substrate contained three different concentrations of urine (urine-free, as-excreted urine-to-feces ratio and double the as-excreted urine-to-feces ratio). Inocula were acclimated to these same urine-to-feces ratios to determine methane production. Results show that both urine-free and as-excreted substrates were not inhibitory to anaerobic inocula. Anaerobic microorganisms can be readily acclimated to substrate with double the as-excreted urine concentration, which contained nitrogen concentrations up to 7.20 g/L. Cumulative methane production reached similar levels in the batch tests, regardless of the substrate urine concentration.     

Laccase mediated biodegradation of 2,4-dichlorophenol using response surface methodology

The effects of different environmental parameters, i.e., pH, temperature, time and enzyme concentration on the biodegradation of 2,4-dichlorophenol (2,4-DCP) in aqueous phase was evaluated with laccase from Pleurotus sp. using response surface methodology (RSM) in the present investigation. The Box-Behnken design of experiments was used to construct second order response surfaces with the investigated parameters. It was observed that the maximum degradation efficiency of approximately 98% was achieved at pH 6, temperature of 40 degrees C, time 9h and an enzyme concentration of 8IUml(-1). The adequacy of the model was confirmed by the coefficient of multiple regression, R(2) and adjusted R(2) which were adjudged to be 87.9% and 73.6%, respectively indicating a reasonably good model for practical implementation. Despite the fact that many successful attempts have been taken in the past for biodegradation of 2,4-DCP using whole cells, the present study emphasizes the fastest biodegradation of 2,4-DCP, a potent xenobiotic compound.     

Genotoxicity assessment of acute exposure of chlorpyrifos to freshwater fish Channa punctatus (Bloch) using micronucleus assay and alkaline single-cell gel electrophoresis

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothioate) is one of the organophosphate pesticides widely used in agricultural practices throughout world and irreversible inhibitor of cholinesterase in all animal species. Limited efforts have been made to study acute genotoxic effects of chlorpyrifos (CPF) in different tissues of fish using genotoxic biomarkers. Therefore, the present investigation was aimed to study the induction of DNA damage by CPF in freshwater teleost fish Channapunctatus using micronucleus assay (MN assay) and alkaline single-cell gel electrophoresis (comet assay). The value of LC(50) - 96 h of CPF was determined as 811.98 microgl(-1) for C. punctatus, in a semi-static system and on the basis of LC(50) value three acute concentrations viz., 203, 406 and 609 microgl(-1) were determined. The fishes were exposed to the different concentrations of CPF for 96 h and samplings were done at regular intervals for assessment of the MN frequencies and DNA damage. In general, significant effects (P<0.01) from both concentrations and time of exposure were observed in exposed fishes. It was found that the micronucleus induction was highest on 96 h at all concentrations in the peripheral blood. Similar trend was observed for the DNA damage measured in terms of the percentage of tail DNA in the lymphocyte and gill cells. This study explored the combined use of micronucleus assay and comet assay for in vivo laboratory studies using fresh water fish for screening the genotoxic potential of xenobiotics.