EXAFS study of adsorbed Cu(II) on fly ashes with different residual carbon contents.

This work studied the speciation of copper species adsorbed onto the surface of fly ash using X-ray absorption spectroscopy (XAS). Experimental results verified that the chemical bond between Cu(II) and the surface of the fly ash was Cu-O. The data set was optimally fitted into the two atomic shells: the first shell containing O atoms and the second shell containing Cu atoms. The extended X-ray absorption fine structure (EXAFS) data also show that, in the first shell, about 2.03-2.41 nearest oxygen atoms surround the center Cu atom with a Cu-O bond distance of 1.96-1.99 A. The results further demonstrated that the bond distance slightly increased with an increasing carbon content of the fly ash.     

Degradation mechanisms of 4-chlorophenol in a novel gas-liquid hybrid discharge reactor by pulsed high voltage system with oxygen or nitrogen bubbling

The effect of gas bubbling on the removal efficiency of 4-chlorophenol (4-CP) in aqueous solution has been investigated using a novel pulsed high voltage gas-liquid hybrid discharge reactor, which generates gas-phase discharge above the water surface simultaneously with the spark discharge directly in the liquid. The time for 100% of 4-CP degradation in the case of oxygen bubbling (7 min) was much shorter than that in the case of nitrogen bubbling (25 min) as plenty of hydrogen peroxide and ozone formed in oxygen atmosphere enhanced the removal efficiency of 4-CP. Except for the main similar intermediates (4-chlorocatechol, hydroquinone and 1,4-benzoquinone) produced in the both cases of oxygen and nitrogen bubbling, special intermediates (5-chloro-3-nitropyrocatechol, 4-chloro-2-nitrophenol, nitrate and nitrite ions) were produced in nitrogen atmosphere. The reaction pathway of 4-CP in the case of oxygen bubbling was oxygen/ozone attack on the radical hydroxylated derivatives of 4-CP. However, in the case of nitrogen bubbling, hydroxylation was the main reaction pathway with effect of N atom on degradation of 4-CP.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

Immobilization of lead in contaminated firing range soil using biochar

Soybean stover-derived biochar was used to immobilize lead (Pb) in military firing range soil at a mass application rate of 0 to 20 wt.% and a curing period of 7 days. The toxicity characteristic leaching procedure (TCLP) was performed to evaluate the effectiveness of the treatment. The mechanism responsible for Pb immobilization in military firing range soil was evaluated by scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray absorption fine structure (XAFS) spectroscopy analyses. The treatment results showed that TCLP Pb leachability decreased with increasing biochar content. A reduction of over 90 % in Pb leachability was achieved upon treatment with 20 wt.% soybean stover-derived biochar. SEM-EDX, elemental dot mapping and XAFS results in conjunction with TCLP leachability revealed that effective Pb immobilization was probably associated with the pozzolanic reaction products, chloropyromorphite and Pb-phosphate. The results of this study demonstrated that soybean stover-derived biochar was effective in immobilizing Pb in contaminated firing range soil.     

Study on the mechanism of action between dimethyl phthalate and herring sperm DNA at molecular level

Dimethyl phthalate (DMP), a typical phthalic acid ester, is widespread in the environment and causes extensive concern due to its adverse effects on human health. To understand the genotoxicity of DMP at molecular level, the toxic interaction of DMP with herring sperm (hs) deoxyribonucleic acid (DNA; hs-DNA) was investigated in vitro under simulated physiological conditions using multi-spectroscopic techniques and a molecular modeling method. The results of Ultraviolet-Visible absorption spectroscopy, fluorescence emission spectroscopy, and circular dichroism spectra indicated that DMP interacts with hs-DNA in a groove-binding mode that changes the double helical structure of DNA. The binding constant and the number of binding sites calculated from the fluorescence quenching data were 565.718 L mol^?1 and 0.7872, respectively. A molecular modeling study revealed that DMP tends to bind with DNA in the A-T-rich regions of minor groove and that hydrogen bonding and van der Waals forces play main roles in the interaction. This research can help to elucidate the mechanism of DMP toxicity in vivo.     

Elucidation of lead-induced oxidative stress in Talinum triangulare roots by analysis of antioxidant responses and DNA damage at cellular level

Hydroponic experiments were performed with Talinum triangulare (Jacq.) Willd. focusing the root cellular biochemistry with special emphasis on DNA damage, structural, and elemental analyses in Pb(NO₃)₂ exposed with 0, 0.25, 0.5, 0.75, 1.0, and 1.25 mM for 7 days. Lead (Pb) increased reactive oxygen species production, lipid peroxidation, protein oxidation, cell death, and DNA damage and decreased the protein content in a dose-dependent manner. Likewise, a dose-dependent induction of antioxidative enzymes superoxide dismutase and catalase by Pb was evident. Ascorbate peroxidase on the other hand responded biphasically to Pb treatments by showing induction at low (0.25 and 0.50) and repression at high (0.75–1.25 mM) concentrations. The estimation of proline content also indicated a similar biphasic trend. Scanning electron microscope and energy-dispersive X-ray spectroscopy analysis showed that 1.25 mM Pb treatment resulted in ultrastructural modifications in roots and stem tissue that was marked by the change in the elemental profile. The findings pointed to the role of oxidative stress in the underlying Pb phytotoxicity and genotoxicity in T. triangulare.     

Removal of NOx from flue gas with iron filings reduction following complex absorption in ferrous chelates aqueous solutions

A novel process for removal of nitrogen oxides (NOx) from flue gases with iron filings reduction following complex absorption in iron-ethylenediaminetetraacetic acid aqueous solution is proposed. The reaction mechanism involved in the process is discussed briefly. The parameters influencing the process, including the concentration of ferrous chelates, initial pH, amount of iron filings, temperature, flow rate of the flue gas, and inlet nitric oxide concentration and oxygen content of the flue gas, are researched in detail. The optimal NOx removal conditions are established. The regeneration and circular utilization of the absorption solution also is studied.     

Removal of nitrogenous compounds by catalytic wet air oxidation. Kinetic study

Aqueous wastes containing organic pollutants can be efficiently treated by wet air oxidation (WAO), i.e. oxidation by molecular oxygen in the liquid phase, under high temperature (200-325 degrees C) and pressure (up to 150 bar). However, organic nitrogen can be relatively resistant to oxidation and can be harmful to the environment. In the course of treatment, organic nitrogen (N-Org) is converted into ammonia (NH(3)), while organic carbon (C-Org) is converted mainly into carbon dioxide (CO(2)). This can be done without catalysts. In the presence of Mn/Ce composite oxides, it is possible to transform ammonia into molecular nitrogen at a temperature close to 260 degrees C. The direct conversion of organic nitrogen into molecular nitrogen also can be achieved using the same catalyst. This paper discusses the results obtained during the treatment of nitrogenous compounds like aniline, nitrophenol, beta-alanine and ammonia. Laboratory investigations were conducted in a stirred batch reactor with Mn/Ce composite oxides as catalysts. Very limited amounts of nitrites and nitrates were observed with amines, but more significant quantities were found with nitro-compounds. The kinetics of oxidation of ammonia, organic compounds, and more particularly aniline, were investigated. The treatment of a real waste (process wastewater) was also investigated. The dependence of the transformation rate on various parameters (amount of catalyst, temperature, etc.) was established. The rates of oxidation are described by first-order kinetic laws with respect to the various nitrogen species (aniline, NH(3)). Several parallel pathways are considered for the transformation of organic nitrogen, amongst which is an interaction with the catalyst surface. The orders with respect to oxygen and catalyst are established.     

Re-evaluation of the conformational structure of sulfadiazine species using NMR and ab initio DFT studies and its implication on sorption and degradation

In the environment, the sorption and the degradation of organic pollutants are of increasing interest. The investigation of the chemical structures provides a basis for the development of a suitable binding model approach and for the mechanistic understanding of the chemical fate processes. The aim of this study was the identification of different species of the antibiotic compound sulfadiazine (SDZ) using (1)H and (13)C NMR experiments and ab initio density functional theory (DFT) calculations. In the neutral, aprotic solvent dimethylsulfoxide-d(6) (DMSO-d(6)), a new sulfadiazine structure containing an O-H-N hydrogen bond was identified. In the protic solvent water-d(2) and in dependence on pH and the position of the amidogen hydrogen atom nine possible SDZ conformations were analyzed and five structures were identified. Good conformity between theory and calculation of (1)H NMR was observed. Unfortunately, (13)C NMR is not sensitive enough for comparison and differentiation. In order to verify the identified structures, additional NBO/NLMO (natural localized molecular orbital) analyses were conducted (calculation of net atomic charges, bond polarity, atomic valence, and electron delocalization). Finally, conformation optimizations were performed in order to investigate the stability of the SDZ species. We showed that SDZ contains no S=O double bond, but that it has two S-O single bonds. Surprisingly, negative charges were observed at the pyrimidine nitrogen atom. With these results, the known structure of SDZ was revised. Studies of the geometrical structure and the torsion angles showed that SDZ is very flexible and can be easily fitted to the sorbent. These observations would explain the strong sorbance and hence the rapid formation of non-extractable residues in the environment because SDZ acts as a strong ligand. These results show that that the sulfonamide hydrogen is important for the biological activity but the pyrimidine nitrogen and the sulfonamide oxygen is responsible for the sorbance in environment.     

Characteristics of electrolysis, ozonation, and their combination process on treatment of municipal wastewater.

The characteristics of municipal wastewater treatment by electrolysis, ozonation, and combination processes of electrolysis and aeration using three gaseous species (nitrogen [N2], oxygen [O2], and ozone [O3]) were discussed in this research using ruthenium oxide (RuO2)-coated titanium anodes and stainless-steel (SUS304) cathodes. Electrolysis and electrolysis with nitrogen aeration were characterized by a rapid decrease in 5-day biochemical oxygen demand (BODs) and total nitrogen and a slow decrease in chemical oxygen demand (COD). In contrast, ozonation, electrolysis with oxygen aeration, and electrolysis with ozone aeration were characterized by transformation of persistent organic matter to biodegradable matter and preservation of total nitrogen. The best energy efficiency in removing BOD5 and total nitrogen was demonstrated by electrolysis, as a result of direct anodic oxidation and indirect oxidation with free chlorine produced from the chloride ion (Cl-) at the anodes. However, electrolysis with ozone aeration was found to be superior to the other processes, in terms of its energy efficiency in removing COD and its ability to remove COD completely, as a result of hydroxyl radical (*OH) production via cathodic reduction of ozone.     

Effects of lead and cadmium nitrate on biomass and substrate utilization pattern of soil microbial communities

A study was conducted to evaluate the effects of different concentrations of lead (Pb) and cadmium (Cd) applied as their nitrates on soil microbial biomass carbon (C(mic)) and nitrogen (N(mic)), and substrate utilization pattern of soil microbial communities. The C(mic) and N(mic) contents were determined at 0, 14, 28, 42 and 56 days after heavy metal application (DAA). The results showed a significant decline in the C(mic) for all Pb and Cd amended soils from the start to 28 DAA. From 28 to 56 DAA, C(mic) contents changed non-significantly for all other treatments except for 600 mgkg(-1) Pb and 100 mgkg(-1) Cd in which it declined significantly from 42 to 56 DAA. The N(mic) contents also decreased significantly from start to 28 DAA for all other Pb and Cd treatments except for 200 mgkg(-1) Pb which did not show significant difference from the control. Control and 200 mgkg(-1) Pb had significantly lower soil microbial biomass C:N ratio as compared with other Pb treatments from 14 to 42 DAA, however at 56 DAA, only 1000 mgkg(-1) Pb showed significantly higher C:N ratio compared with other treatments. No significant difference in C:N ratio for all Cd treated soils was seen from start to 28 DAA, however from 42 to 56 DAA, 100 mgkg(-1) Pb showed significantly higher C:N ratio compared with other treatments. On 56 DAA, substrate utilization pattern of soil microbial communities was determined by inoculating Biolog ECO plates. The results indicated that Pb and Cd addition inhibited the functional activity of soil microbial communities as indicated by the intensity of average well color development (AWCD) during 168 h of incubation. Multivariate analysis of sole carbon source utilization pattern demonstrated that higher levels of heavy metal application had significantly affected soil microbial community structure.     

Phytoremediation potential of Pteris vittata L. under the combined contamination of As and Pb: beneficial interaction between As and Pb

The frequent co-existence of arsenic (As) and lead (Pb) necessitates the investigation of clean-up technologies for multi-metal(loid)s. Field survey and hydroponic experiments were conducted to elucidate the co-accumulation of As and Pb in Pteris vittata L. The P. vittata population isolated from a Pb–Zn mine in Yunnan province, China is a potential extractor of As and Pb co-contamination. Hydroponic experiment found that the highest frond As and Pb concentrations in mining population of P. vittata reached 12.2 and 0.99 g kg^?1, respectively. The interaction between As and Pb in P. vittata was further more disclosed. Pb (2 mg L^?1) improved the frond As concentration by 60 to 150 % in mining populations of P. vittata. Micro-X-ray absorption spectroscopy indicated that under the combined exposure of As and Pb, the As content in the rhizoid epidermis increased by about 10-fold, and the As(V) percentage increased in each rhizoid tissue, as compared with that under As exposure alone. The co-absorption of As and Pb on the epidermis and the enhanced transportation of As(V) from epidermis into the rhizoid were suggested to contribute to the increased As accumulation.     

Removing nitric oxide from flue gas using iron(II) citrate chelate absorption with microbial regeneration

The addition of metal chelates such as Fe(II)EDTA or Fe(II)Cit to wet flue gas desulfurization systems has been shown to increase the amount of NO(x) absorption from gas streams containing SO(2). This paper attempts to demonstrate the advantage of not only using Fe(II)Cit chelate to absorb nitrogen oxides from flue gas but also the advantage gained from adding microorganisms to the system. Two distinct classes of microorganisms are needed: denitrifying and iron-reducing bacteria. The presence of oxygen in flue gas will affect the absorption efficiency of NO by Fe(II)Cit chelate. The oxidation of Fe(II) can be slowed with the help of bacteria in two ways: bacteria can serve to directly reduce Fe(III) to Fe(II) or they can serve to keep levels of dissolved oxygen in the solution low. As a result, after NO absorption, Fe(II)(Cit)NO will be reduced by denitrifying bacteria to Fe(II)Cit while Fe(III) is reduced by anaerobic bacteria back to Fe(II). Our experiments have shown that the implementation of our protocol allowed for an NO reduction rate constant increase from standard levels of 0.0222-0.100 m Mh(-1) with inlet NO changed from 250 to 1000 ppm. We have also found that total Fe concentration tends to decrease after prolonged periods of operation due to the loss of some Fe to the formation of Fe(OH)(3) that settles together with the sludge at the bottom of bioreactor tank.     

Nitrogen Dioxide Absorption and Sulfide Oxidation in Aqueous Sulfide

ABSTRACT

Rates of nitrogen dioxide (NO₂) absorption and sulfide oxidation were measured in a highly characterized stirred cell contactor at 55 °C, with O₂ present in the gas phase. The rate constant of the reaction between NO₂ and sul-fide at 55 °C was determined to be 26.4 x10⁵ M^-1sec^-1. A reaction mechanism was proposed that is consistent with the kinetic data. NO₂ absorption initiates sulfide oxidation in the presence of oxygen. The rate of sulfide oxidation increased with sulfide and oxygen concentration and with the rate of NO₂ absorption. Furthermore, thiosulfate was an effective inhibitor of sulfide oxidation.     

Genotypic and environmental variation in chromium, cadmium and lead concentrations in rice

Genotypic and environmental variation in Cr, Cd and Pb concentrations of rice grains and the interaction between these metals were investigated by using 138 rice genotypes grown in three contaminated soils. There were significant genotypic differences in the three heavy metal concentrations of rice grains, with the absolute difference among 138 genotypes in grain Cr, Cd and Pb concentrations being 24.5-, 9.1- and 23.8-folds, respectively, under the slightly contaminated soil (containing 4.61mgkg(-1) Cr, 1.09mgkg(-1) Cd and Pb 28.28mgkg(-1), respectively). A highly significant interaction occurred between genotype and environment (soil type) in the heavy metal concentrations of rice grains. Cr concentration in rice grains was not correlated with Cd and Pb concentration. However, there was a significant correlation between Cd and Pb in slightly and highly contaminated soils. The results suggest the possibility to develop the rice cultivars with low Cd and Pb concentrations in grain.     

Removal of NOx from Flue Gas with Iron Filings Reduction Following Complex Absorption in Ferrous Chelates Aqueous Solutions

Abstract

A novel process for removal of nitrogen oxides (NO_x) from flue gases with iron filings reduction following complex absorption in iron-ethylenediaminetetraacetic acid aqueous solution is proposed. The reaction mechanism involved in the process is discussed briefly. The parameters influencing the process, including the concentration of ferrous chelates, initial pH, amount of iron filings, temperature, flow rate of the flue gas, and inlet nitric oxide concentration and oxygen content of the flue gas, are researched in detail. The optimal NO_x removal conditions are established. The regeneration and circular utilization of the absorption solution also is studied.     

Is tree growth reduction related to direct foliar injuries or soil chemistry modifications?

In the context of intense emissions causing atmospheric pollution, tree growth reductions could be related to soil chemistry modifications or direct foliar injuries. To verify these hypotheses, mineral soils were sampled in an area (Murdochville, Canada) where previous studies had demonstrated that tree growth was impacted by smelter emissions and that forest floor lead concentrations could be used as a proxy for atmospheric pollutant depositions. Samples were analysed for Al, Pb (concentrations and isotope ratios), basic cations (Ca, K, P, and Mg) and Zr. Mass balance calculations were performed on soil profiles to assess vertical migration of elements. Pb concentrations in litter diminished gradually with distance from the smelter. The Pb isotope ratios in these organic soil layers were close to those measured in the Murdochville ores. These patterns were not encountered in mineral soil layers. Pb isotope ratios in these layers were close to those measured in uncontaminated geological materials, and Pb concentrations and basic cation depletions were not related to the proximity of the smelter. Growth reduction was closely associated with litter Pb concentrations, which were used as a proxy for atmospheric deposition, but was not correlated with any elemental concentration or cation depletion measured in mineral soil layers. Our overall results suggest that trees responded mainly to direct atmospheric emissions, which caused foliar damage, rather than to soil chemistry modifications.     

Effects of nitrogen and oxygen on biofilter performance

Three laboratory-scale biofilters packed with inert material were used to study the nitrogen and oxygen requirements for biofiltration of methanol. Mixtures of methanol with inorganic nitrogen (NH3 or NO3) at nitrogen-to-carbon (N:C) ratios ranging from 0.015 to 0.4 were employed to reveal nitrogen effects on biofiltration. In the oxygen study, mixtures of air and oxygen at different oxygen contents were used. At low nitrogen levels, the removal rate increased with increasing N:C ratio for both NH3 and NO3. However, at high concentrations, NH3 had an inhibitory effect on biodegradation while the removal rate reached a plateau at high NO3 concentrations. Biofiltration with 63% oxygen in the inlet gas stream increased the maximum removal rate from 120 to 145 g/m3/hr after 3 days in comparison with biofiltration with air. However, a further increase in oxygen content up to 80% did not lead to a further improvement in biofilter performance, suggesting that both oxygen and biofilm thickness can be the relevant factors limiting biofilter performance and creating the plateau in removal rates at high loadings.