Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

Effects of heavy metals and nitroaromatic compounds on horseradish glutathione S-transferase and peroxidase

Glutathione S-transferase (GST) and peroxidase (POX) activities have a direct relation to the effect of stress on plant metabolism. Changes in the activities of the enzymes were therefore studied. Horseradish hairy roots were treated by selected bivalent ions of heavy metals (HMs) and nitroaromatic compounds (NACs). We have shown differences in GST activity when assayed with substrates 1-chloro-2,4-dinitrobenzene (CDNB) and 1,2-dichloro-4-nitrobenzene (DCNB). The conjugation of DCNB catalysed by GST was inhibited in all roots treated with HMs as compared to non-treated roots, whereas NACs caused induction of the activity in dependence on the exposition time and concentration of compounds. The conjugation of CDNB by GST was not affected to the same extent. The increase of GST activity was determined in cultures treated by nickel (0.1 mM) and diaminonitrotoluenes (DANTs, 0.1 mM) for 6 h, whereas the roots treated by 2,4,6-trinitrotoluene (TNT), 4-amino-2,6-dinitrotoluene (ADNT) and dinitrotoluene (DNT, 1.0 mM) needed 27 h treatment to induce the activity. The POX activity of cultures treated by HMs was inhibited to 17-35% in comparison to non-treated cultures. The POX activity of roots treated by TNT (0.1 and 1.0 mM) for 6 and 27 h and by ADNT (0.1 and 1.0 mM) for 6 h was inhibited. A partial increase of POX activity was measured in roots treated by all NACs for 27 h. The content of oxidized glutathione (GSSG) and reduced glutathione (GSH) in the roots differed significantly. It was followed as a symptom of the stress reaction of the plant metabolism to the effect of NACs and HMs.     

Improved phosphorus use efficiency in agriculture: a key requirement for its sustainable use

Mineral phosphorus (P) fertilizers processed from fossil reserves have enhanced food production over the past 50 years and, hence, the welfare of billions of people. Fertilizer P has, however, not only been used to lift the fertility level of formerly poor soils, but also allowed people to neglect the reuse of P that humans ingest in the form of food and excrete again as faeces and urine and also in other organic wastes. Consequently, P mainly moves in a linear direction from mines to distant locations for crop production, processing and consumption, where a large fraction eventually may become either agronomically inactive due to over-application, unsuitable for recycling due to fixation, contamination or dilution, and harmful as a polluting agent of surface water. This type of P use is not sustainable because fossil phosphate rock reserves are finite. Once the high quality phosphate rock reserves become depleted, too little P will be available for the soils of food-producing regions that still require P supplements to facilitate efficient utilization of resources other than P, including other nutrients. The paper shows that the amounts of P applied in agriculture could be considerably smaller by optimizing land use, improvement of fertilizer recommendations and application techniques, modified livestock diets, and adjustment of livestock densities to available land. Such a concerted set of measures is expected to reduce the use of P in agriculture whilst maintaining crop yields and minimizing the environmental impact of P losses. The paper also argues that compensation of the P exported from farms should eventually be fully based on P recovered from ‘wastes’, the recycling of which should be stimulated by policy measures.     

Degradation of ethinyl estradiol by nitrifying activated sludge

Degradation of ethinyl estradiol (EE2) by nitrifying activated sludge was studied with micro-organisms grown in a reactor with feedback of sludge fed with only a mineral salts medium containing ammonium as the sole energy source. Ammonium was oxidised by this sludge at a rate of 50 mg NH4+ g(-1) DW h(-1). This activated sludge was also capable of degrading EE2 at a maximum rate of 1 microg g(-1) DW h(-1). Using sludge with an insignificant nitrifying capacity of 1 mg NH4+ g(-1) DW h(-1), no degradation of EE2 was detected. Oxidation of EE2 by nitrifying sludge resulted in the formation of hydrophilic compounds, which were not further identified. Most probably degradation by nitrifying sludge results in a loss of estrogenic activity, as hydroxylated derivatives of EE2 are known to have a substantially lower pharmacological activity than EE2.     

Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.     

The Influence of Mycorrhiza on Uranium and Phosphorus Uptake by Barley Plants from a Field-contaminated Soil (7 pp)

Background Recent studies indicated that arbuscular mycorrhizal fungi (AMF) play important roles in plant accumulation of uranium (U) from contaminated environments, but the impacts of fertilization practices on functioning of the symbiotic associations, which are crucial factors influencing plant nutrition and growth responses to mycorrhiza, have rarely been considered. Materials and Methods In a greenhouse experiment, a bald root barley mutant (brb) together with the wild type (wt) were used to test the role of root hairs and AMF in uranium (U) uptake by host plants from a U contaminated soil. Nil, 20 and 60 mg KH2PO4-P kg–1 soil were included to investigate the influences of phosphorus (P) fertilization on plant growth and accumulation of U. Results Dry matter yield of barley plants increased with increasing P additions and wt produced significantly higher dry weight than brb. Mycorrhiza markedly improved dry matter yield of both genotypes grown at nil P, whereas only brb responded positively to mycorrhiza at 20 mg P kg-1. At the highest P level, mycorrhiza resulted in growth depressions in both genotypes, except for the roots of wt. In general, plant P concentrations increased markedly with increasing P additions and in response to mycorrhiza. Mycorrhiza and P additions had no significant effects on shoot U concentrations. However, root U concentrations in both genotypes were significantly increased by mycorrhiza. On the other hand, shoot U contents increased with increasing P levels, while 20 mg P kg-1 stimulated, but 60 mg P kg-1 marginally affected the U accumulation in roots. Root length specific U uptake was moderately enhanced both by root hairs and strongly enhanced by mycorrhiza. Moreover, non-inoculated plants generally had higher shoot-root ratios of U content than the corresponding inoculated controls. Conclusion Our study shows that AMF and root hairs improves not only P acquisition but also the root uptake of U, and mycorrhiza generally decreases U translocation from plant root to shoot. Hence, mycorrhiza is of potential use in the phytostabilization of U contaminated environments. Perspectives The complex impacts of P on U accumulation by barley plants suggested that U behavior in mycorrhizosphere and translocation along the soil-fungi-plant continuum as affected by fertilization practices deserve extensive studies for optimizing the function of mycorrhizal associations for phytoremediation purposes.     

Removal of PCBs from wastewater using fly ash

Liquids and sludges containing polychlorinated biphenyls (PCBs) can be treated to concentrate the PCBs in a solid residue. The latter can then be handled to destroy the PCBs. A study on sorption kinetics of PCBs on fly ash was conducted in controlled batch systems. TCB and HeCB are removed at 25 degrees C by adsorption on fly ash up to 97% at pH 7, with an adsorbent dose of 5 g/l. An examination of the thermodynamic parameters shows that the adsorption of TCB and HeCB by fly ash is a process occurring spontaneously at ambient conditions. Activation energies for the sorption process ranged between 5.6 and 49.1 kJ/mol. It was observed that the rate at which TCB and HeCB are adsorbed onto fly ash showed a diffusion limitation. The uptake rate of TCB and HeCB increases with increasing initial concentration and gradually tends to a constant value. A decrease in the adsorption of TCB and HeCB was observed when interfering ions and other PCB congeners were present. Changing the pH in the aqueous solution from 2 to 10 had no effect on the adsorption process. Overall, fly ash can be used for an efficient removal of PCBs from several aqueous solutions.     

Cyanide Removal by Chinese Vegetation. Quantification of the Michaelis-Menten Kinetics (6 pp)

Background Little is known about metabolism rates of environmental chemicals by vegetation. A good model compound to study the variation of rates among plant species is cyanide. Vascular plants possess an enzyme system that detoxifies cyanide by converting it to the amino acid asparagine. Knowledge of the kinetic parameters, the half-saturation constant (Km) and the maximum metabolic capacity (vmax), is very useful for enzyme characterization and biochemical purposes. The goal of this study is to find the enzyme kinetics (KM and vmax) during cyanide metabolism in the presence of Chinese vegetation, to provide quantitative data for engineered phytoremediation, and to investigate the variation of metabolic rates of plants. Methods Detached leaves (1.0 g fresh weight) from 12 species out of 9 families were kept in glass vessels with 100 mL of aqueous solution spiked with potassium cyanide at 23°C for 28 h. Four different treatment concentrations of cyanide were used, ranging from 0.44 to 7.69 mg CN/L. The disappearance of cyanide from the aqueous solution was analyzed spectrophotometrically. Realistic values of the half-saturation constant (KM) and the maximum metabolic capacity (vmax) were estimated by a computer program using non-linear regression treatments. As a comparison, Lineweaver-Burk plots were also used to estimate the kinetic parameters. Results and Discussion The values obtained for KM and vmax varied with plant species. Using non-linear regression treatments, values of vmax and KM were found in a range between 6.68 and 21.91 mg CN/kg/h and 0.90 to 3.15 mg CN/L, respectively. The highest vmax was by Chinese elder (Sambucus chinensis), followed by upright hedge-parsley (Torilis japonica). The lowest vmax was demonstrated by the hybrid willow (Salix matssudana x alba). However, the highest KM was found in the water lily (Nymphea teragona), followed by the poplar (Populus deltoides Marsh). The lowest KM was demonstrated by corn (Zea mays L.). The values of vmax were normally distributed with a mean of 13 mg CN/kg/h. Conclusions Significant removal of cyanide from aqueous solution was observed in the presence of plant materials without phytotoxicity, even at high doses of cyanide. This gives rise to the conclusion that the Chinese plant species used in this study are all able to efficiently metabolize cyanide, although with different maximum metabolic capacities. A second conclusion is that the variation of metabolism rates between species is small. All these plants had a similar KM, indicating the same enzyme is active in all plants. Recommendations and Outlook Detoxification of cyanide with trees seems to be a feasible option for cleaning soils and water contaminated with cyanide. For phytoremediation projects, screening appropriate plant species adapted to local conditions should be seriously considered. More chemicals should be investigated to find common principles of the metabolism of environmental chemicals by plants.     

Atmospheric BTEX concentrations in the vicinity of the crude oil refinery of the Baltic region

Among chemical industries, petroleum refineries have been identified as large emitters of a wide variety of pollutants. Benzene, toluene, ethylbenzene, and xylene (BTEX) form an important group of aromatic volatile organic compounds (VOCs) because of their role in the troposphere chemistry and the risk posed to human health. A very large crude oil refinery of the Baltic States (200,000 bbl/day) is situated in the northern, rural part of Lithuania, 10 km from the town of Ma?eikiai (Lithuania). The objectives of this study were: (1) to determine of atmospheric levels of BTEX in the region rural and urban parts at the vicinity of the crude oil refinery; and (2) to investigate the effect of meteorological parameters (wind speed, wind direction, temperature, pressure, humidity) on the concentrations measured. The averaged concentration of benzene varied from 2.12 ppbv in the rural areas to 2.75 ppbv in the urban areas where the traffic was determined to be a dominant source of BTEX emissions. Our study showed that concentration of benzene, as strictly regulated air pollutant by EU Directive 2008/50/EC, did not exceed the limit of 5 ppbv in the region in the vicinity of the crude oil refinery during the investigated period. No significant change in air quality in the vicinity of the oil refinery was discovered, however, an impact of the industry on the background air quality was detected. The T/B ratio (0.50-0.81) that was much lower than 2.0, identified other sources of pollution than traffic.     

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.