Temperature dependence of nickel stabilization in inorganic oxide matrices

Scanning electron microscopy, X-ray diffractometry, X-ray absorption spectroscopy, and other means are used to investigate the effect of thermal treatment temperature, 105-1100 degrees C, on the immobilization of nickel (Ni) by the inorganic oxides of latosol. Ni is more firmly immobilized by the latosol with increasing temperature. Spectral analyses indicate that a shoulder toward the edge-jump appears in the spectra of X-ray absorption near-edge structure for the samples heated at 900 and 1100 degrees C. Moreover, the intensity of the main peak at the edge increases with higher temperature; this information indicates the distortion of the divalent nickel [Ni(II)] environment in the samples heated at 900 and 1100 degrees C. Nevertheless, the distortion is absent from the samples heated at 105 and 500 degrees C. The fact of the distortion of the Ni(II) environment suggests the occurrence of a chemical reaction between the Ni compound and the inorganic matrices of the latosol soil during the heating process at 900 and 1100 degrees C. In addition, the extended X-ray absorption fine structure results correspond well to the X-ray absorption near-edge structure results; the former are supportive of the occurrence of a distorted Ni(II) environment in the samples heated at 900 and 1100 degrees C. The wet-chemistry results show that the samples heated at 900-1100 degrees C leach less Ni than the 105-500 degrees C samples do. The change of the Ni environment is related to the observation that less Ni is leached from the samples heated at 900-1100 degrees C. Furthermore, the pore closing phenomenon is observed only in the 1100 degrees C sample; this phenomenon corresponds with the fact that the 1100 degrees C sample leaches less Ni than the 900 degrees C sample does.     

Heavy metals affect the coelomocyte-bacteria balance in earthworms: environmental interactions between abiotic and biotic stressors

Three-day dermal exposure of Dendrobaena veneta to metal ions differentially disrupts the immunocompetence/pathogen balance. Zn does not accumulate in the earthworm body, Cu accumulation is temperature-independent while Cd accumulation is stronger at 22 degrees C than at 10 degrees C. During in vitro incubation with metal ions at 22 degrees C, growth of coelom-derived bacteria is enhanced by Zn, but significantly or almost completely inhibited by Cu or Cd. In contrast, under in vivo conditions at 22 degrees C, bacterial load is decreased only after Cd exposure, but increased after Zn and Cu exposures. At 10 degrees C bacteria growth is almost completely inhibited in all groups except Cu-treated animals. Coelomocyte number is unaffected in animals exposed to Zn, but significantly decreased after exposure to Cd (at 22 degrees C) and Cu (at 22 degrees C and 10 degrees C) with concomitant changes of amoebocyte-to-eleocyte ratio in favour of amoebocytes. Metal exposure up-regulates expression of metallothioneins in coelomocytes, mainly amoebocytes.     

Quick determination of malodor-causing fatty acids in manure by capillary electrophoresis

The analysis of odor components in livestock waste has been extensively studied. Past research has identified volatile fatty acids, especially from C3 to C6, as indicators of malodor. Originally, the odorous components were analyzed by gas chromatography after a tedious absorption and troublesome extraction procedure or by a subjectively olfactory system or sense of smell. Thus, there is a need for the development of highly specific, quantitative analytical methods. In this research, a comprehensive liquid manure analysis approach-capillary electrophoresis (CE) with a systematic optimization procedure-was adopted to measure the concentration of propanoic acid (C2H5COOH, C3), butyric acid (C3H7COOH, C4), valeric acid (C4H9COOH, C5) and caproic acid (C5H11COOH, C6) in swine manure. Liquid samples after filtration were injected into CE directly. The following condition is finally proposed: fused-silica capillary, effective length 40 cm, 50 microm I.D.; buffer, 20 mM Tris and 10 mM p-anisate, pH 8.0; voltage 30 kV; temperature 25 degrees C. The results showed that CE provided a quantitative analysis of volatile fatty acids in liquid manure at the ppm level with minimum sample needed (nanoliter). Moreover, the use of CE is a timesaving technique; one measurement for the separation of those VFAs could be completed within 10 min.     

Temperature Dependence of Nickel Stabilization in Inorganic Oxide Matrices

Abstract

Scanning electron microscopy, X‐ray diffractometry, X‐ray absorption spectroscopy, and other means are used to investigate the effect of thermal treatment temperature, 105–1100 °C, on the immobilization of nickel (Ni) by the inorganic oxides of latosol. Ni is more firmly immobilized by the latosol with increasing temperature. Spectral analyses indicate that a shoulder toward the edge‐jump appears in the spectra of X‐ray absorption near‐edge structure for the samples heated at 900 and 1100 °C. Moreover, the intensity of the main peak at the edge increases with higher temperature; this information indicates the distortion of the divalent nickel [Ni(II)] environment in the samples heated at 900 and 1100 °C. Nevertheless, the distortion is absent from the samples heated at 105 and 500 °C. The fact of the distortion of the Ni(II) environment suggests the occurrence of a chemical reaction between the Ni compound and the inorganic matrices of the latosol soil during the heating process at 900 and 1100 °C. In addition, the extended X‐ray absorption fine structure results correspond well to the X‐ray absorption near‐edge structure results; the former are supportive of the occurrence of a distorted Ni(II) environment in the samples heated at 900 and 1100 °C. The wet‐chemistry results show that the samples heated at 900–1100 °C leach less Ni than the 105–500 °C samples do. The change of the Ni environment is related to the observation that less Ni is leached from the samples heated at 900–1100 °C. Furthermore, the pore closing phenomenon is observed only in the 1100 °C sample; this phenomenon corresponds with the fact that the 1100 °C sample leaches less Ni than the 900 °C sample does.     

Reduction of hexavalent chromium by ascorbic acid in aqueous solutions

Hexavalent chromium is a priority pollutant in the USA and many other countries. Reduction of Cr(VI) to Cr(III) is environmentally favorable as the latter species is not toxic to most living organisms and also has a low mobility and bioavailability. Reduction of Cr(VI) by ascorbic acid (vitamin C) as a reductant was studied using potassium dichromate solution as the model pollutant. Effects of concentration of vitamin C, pH, temperature, irradiation and reaction time on the reduction of Cr(VI) were examined. Cr(VI) might be reduced by vitamin C not only in acidic conditions but also in weakly alkaline solutions. The reduction of Cr(VI) by vitamin C might occur not only under irradiation but also in the dark. Vitamin C is an important biological reductant in humans and animals, and not toxic. It is water-soluble and can easily permeate through various types of soils. The results indicate that vitamin C could be used in effective remediation of Cr(VI)-contaminated soils and groundwater in a wide range of pH, with or without sunlight.     

Formation characteristics of aerosol particles from pulverized coal pyrolysis in high-temperature environments

The formation characteristics of aerosol particles from pulverized coal pyrolysis in high temperatures are studied experimentally. By conducting a drop-tube furnace, fuel pyrolysis processes in industrial furnaces are simulated in which three different reaction temperatures of 1000, 1200, and 1400 degrees C are considered. Experimental observations indicate that when the reaction temperature is 1000 degrees C, submicron particles are produced, whereas the particle size is dominated by nanoscale for the temperature of 1400 degrees C. Thermogravimetric analysis of the aerosol particles stemming from the pyrolysis temperature of 1000 degrees C reveals that the thermal behavior of the aerosol is characterized by a three-stage reaction with increasing heating temperature: (1) a volatile-reaction stage, (2) a weak-reaction stage, and (3) a soot-reaction stage. However, with the pyrolysis temperature of 1400 degrees C, the volatile- and weak-reaction stages almost merge together and evolve into a chemical-frozen stage. The submicron particles (i.e., 1000 degrees C) are mainly composed of volatiles, tar, and soot, with the main component of the nanoscale particles (i.e., 1400 degrees C) being soot. The polycyclic aromatic hydrocarbons (PAHs) contained in the aerosols are also analyzed. It is found that the PAH content in generated aerosols decreases dramatically as the pyrolysis temperature increases.     

Use of a lux-marked rhizobacterium as a biosensor to assess changes in rhizosphere C flow due to pollutant stress

The flow of carbon from plant roots into soil supports a range of microbial processes and is therefore critical to ecosystem function and health. Pollution-induced stress, which influences rhizosphere C flow is of considerable potential importance, and therefore needs to be evaluated. This paper reports on a method, based on reporter gene technology, for quantifying pollutant effects on rhizosphere C flow. The method uses the lux-marked rhizobacterium Pseudomonas fluorescens, where bioluminescence output of this biosensor is directly correlated with the metabolic activity and reports on C flow in root exudate. Plantago lanceolata was treated with paraquat (representing a model pollutant stress) in a simple microcosm system. The lux-biosensor response correlated closely with C concentrations in the exudate and demonstrated that the pollutant stress increased the C flow from the plantago roots, 24 h after application of the herbicide. The lux-reporter system therefore potentially offers a technique for use in assessing the impact of pollutant stress on rhizosphere C flow through the soil microbial biomass.     

Photocatalytic degradation of N-heterocyclic aromatics—effects of number and position of nitrogen atoms in the ring

This study demonstrates the influences of position, number of nitrogen (N) atoms and –C–N– or –N=N– linkage present in the six membered heterocyclic compounds such as pyridine, pyrazine, and pyridazine on their photocatalytic degradation by Au, Ag, and Fe⁺² deposited TiO₂ photocatalyst. The photodegradation rate of these heterocyclic compounds follow the order pyridine > pyrazine > pyridazine due to the different extent of hydroxylation and difference in position and number of N atoms in the aromatic moiety. The Au photodeposition significantly improved the TiO₂ photoactivity as compared to Ag and Fe⁺² loading. The presence of two N atoms in pyrazine and pyridazine as compared to one N atom in pyridine hamper the nucleophilc attack of OH radicals in comparison to easy hydroxylation of pyridine ring. There is 1 N atom, 4C–C, 1C–N and 1C=N bond in pyridine, 2 N atoms in the 1 and 4 positions, 2C–C, 2C–N bonds and 2C=N bonds in pyrazine, and pyridazine ring contains 2 N atoms in the 1 and 2 positions, 3C–C, 1N–N bond and 2C=N bonds. The bond strength/energy decreases gradually as: C=N– (615 KJ/mol)?>?–N=N– (418 KJ/mol)?>?–C–C– (347 KJ/mol)?>?–C–N– (305 KJ/mol)?>?–N–N– (163 KJ/mol). As pyridine has 1C–N, 1C=N, and no N–N bond, it photodegrades easily as compared to 1 N–N and 2C=N bonds of pyridazine of lowest photodecomposition rate. The improved photoactivity of Au–TiO₂ is explained on the basis of its favorable redox potential, work function, and electron-capturing capacity, etc.     

Early changes in the fatty acid composition of photosynthetic membrane lipids from Populus nigra grown on a metallurgical landfill

We compared the fatty acid composition of leaves taken from poplars on a metal-contaminated landfill, and on the uncontaminated roadside bordering this site. For the first time, it is shown that the percentage of linolenic acid, which is mainly associated with thylakoid lipids, was significantly lower in tree species within the landfill than within the control area. A correlation study was carried out to investigate relationships between the C18:3/(C18:0 + C18:1 + C18:2) fatty acid ratios and the metal contents in soils and leaves. Lead and chromium leaf contents were significantly negatively correlated to this fatty acid ratio. The impact of each of these metals remains difficult to evaluate, but chromium in leaf likely plays a major role in toxicity. In addition, the decrease in the C18:3/(C18:0 + C18:1 + C18:2) fatty acid ratio occurred at low leaf metal content, and therefore it is shown that this ratio can be used as an early indicator of the effect of metals.     

Study of the trace metal ion influence on the turnover of soil organic matter in cultivated contaminated soils

The role of metals in the behaviour of soil organic matter (SOM) is not well documented. Therefore, we investigated the influence of metals (Pb, Zn, Cu and Cd) on the dynamic of SOM in contaminated soils where maize (C4 plant) replaced C3 cultures. Three pseudogley brown leached soil profiles under maize with a decreasing gradient in metals concentrations were sampled. On size fractions, stable carbon isotopic ratio (delta13C), metals, organic carbon and nitrogen concentrations were measured in function of depth. The determined sequence for the amount of C4 organic matter in the bulk fractions: M3 (0.9)>M2 (0.4)>M1 (0.3) is in agreement with a significant influence of metals on the SOM turnover. New C4 SOM, mainly present in the labile coarser fractions and less contaminated by metals than the stabilised C3 SOM of the clay fraction, is more easily degraded by microorganisms.     

Speciation of non-methane hydrocarbons (NMHCs) from anthropogenic sources in Beirut,Lebanon

The chemical composition of emissions from the different anthropogenic sources of non-methane hydrocarbons (NMHC) is essential for modeling and source apportionment studies. The speciated profiles of major NMHC sources in Lebanon, including road transport, gasoline vapor, power generation, and solvent use were established. Field sampling have been carried out by canisters in 2012. Around 67 NMHC (C2 to C9) were identified and quantified by using a gas chromatograph equipped with a flame ionization detector. Typical features of the roadway emissions included high percentages of isopentane, butane, toluene, xylenes, ethylene, and ethyne. Gasoline evaporation profiles included high percentage of the C4–C5 saturated hydrocarbons reaching 59 %. The main compounds of the power generator emissions are related to combustion. Toluene and C8–C9 aromatics were the most abundant species in emissions from paint applications. Finally, the impact of the use of region-specific source profile is tackled regarding the implication on air quality.     

Thermal behavior of PCDD/PCDF in fly ash from municipal incinerators

The effect of thermal treatment of fly ash on the behaviour of PCDD/PCDF was studied in the range between 120 and 600° C. Annealing at 300° C (2 hrs) resulted in an increase of PCDD/PCDF concentration by a factor of 10 to 15. At 600° C degradation to concentrations below 0.1 ng/g is observed.     

Photodegradation of Dyes in Aqueous Solutions containing Fe(III) -hydroxy Complex II. Solar Photodegradation Kinetics

The solar photodegradation of five dyes, C.I. reactive red 2, C.I. reactive blue 4, C.I. reactive black 8, C.I. basic red 13, and C.I. basic yellow 2, were studied in a sunlight/Fe(III)-hydroxy system. It was observed that the photodegradation of these five dyes were pseudo-first order reactions, which has a little difference with the photodegradation kinetics of the dyes with UV-light as the irradiation source. The comparison between the two studies is also conducted.     

Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions

An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment. Therefore, additional study is required to evaluate the full regulatory implications of upgrading air quality models to SAPRC07.     

Photosynthesis and biomass allocation of radish cv. "Cherry Belle" in response to root temperature and ozone

To determine if ozone (O3) and root zone temperature (RZT) affect plant biomass allocation and photosynthesis, radish (Raphanus sativus) plants were grown in controlled environment laboratory chambers in one of four treatments: episodic O3 (average delivery 0.063 mumol mol-1) with RZT at 13 degrees C, episodic O3 (same delivery) with RZT at 18 degrees C, charcoal-filtered air with RZT at 13 degrees C and charcoal-filtered air with RZT at 18 degrees C. O3 reduced total biomass and shoot biomass of radish at 13 degrees C RZT but had no effect at 18 degrees C RZT. Low (13 degrees C) RZT decreased total biomass in both O3 and charcoal-filtered air. RZT had no overall effect on biomass allocation, but O3 lowered root-to-shoot ratios for plants grown at 18 degrees C RZT. Photosynthesis was reduced for plants grown at 18 degrees C RZT and O3, but stomatal conductance was not affected by O3 nor RZT. These results indicate that O3 and low RZT decrease biomass, but that plant photosynthesis is decreased by O3 and warm RZT.     

Changes in lipids and sterols during composting

Pyrolysis-gas (Py-GC) chromatography was used to characterize organic [(diethyl ether (DEE) and chloroform (CHCl3)] extracts of raw and composted duck excreta enriched wood shavings from two finishing cycles (C1 and C2). Materials were collected on days 0, 8 and 23. C1 contained 1.7 % total N while C2 contained 0.9 % total N. Py-GC-MS (mass spectrometry) showed that the extracts contained n-alkanes (C12 to C32), alkenes (C12:1 to C33:1), n-fatty acids (C12 to C28), unsaturated fatty acids (C18:1 and C18:2), and sterols (cholestene, cholestadiene, stigmastene, stigmastadiene, stigmastatriene, cholesterol, stigmastanol, stigmastanone, stigmastadienone, 17-methyl dialkylsulfanyl decahydro-1H-cyclopenta [a] phenanthrene, 17-methyl dialkylsulfanyl dodecahydro-1H-cyclopenta [a] phenanthrene, and 17-methyl-17-dialkylsulfanyl decahydro-1H-cyclopenta [a] phenanthrene). Other components identified were prystene, squalene (precursor of cholesterol), phthalic acid, diphenylpropane, diphenylbut-2-ene and 1,3,6 triphenyl hex-4-ene. Our data showed significant changes in the lipid composition of duck excreta enriched wood shavings during composting, which appeared to be related to the total N content of the system.     

Effects of operating parameters on in situ NH3 emission control during kitchen waste composting and correlation analysis of the related microbial communities

Ammonia emission during composting results in anthropogenic odor nuisance and reduces the agronomic value of the compost due to the loss of nitrogen. Adjusting the operating parameters during composting is an emerging in situ odor control technique that is cheap and highly efficient. The effects of in situ NH₃ emission control were investigated in this study by simultaneously adjusting key operating parameters (such as C/N ratio, aeration rate, and moisture content) during the composting processes (C1–C9). Results showed that the average NH₃ emission concentrations for different treatments were in the order of C1 > C4 > C2 > C5 > C3 > C6 > C7 > C8 > C9. The total content of NH₃ emission (21.02 g/kg) in C9 (C/N ratio = 35, aeration rate = 15 L/min, and moisture content = 60%) was much lower than that (65.95 g/kg) in C1 (C/N ratio = 15, aeration rate = 5 L/min, and moisture content = 60%). The nitrogen loss ratio was 27.36% for C1, while 16.15% for C9. The microbial diversity and abundance in C9 and C1 were compared using high-throughput sequencing. The relationship between NH₃ emission, operating parameters, and the related functional microbial communities was also investigated. Results revealed that Nitrosospira, Nitrosomonas, Nitrobacter, Pseudomonas, Methanosaeta, Rhodobacter, Paracoccus, and Sphingobacterium were negatively related to NH₃ emission. According to the above results, the optimal values for different operating parameters for the in situ NH₃ control during kitchen waste composting were, respectively, moisture content of 70%, C/N ratio of 35, and aeration rate of 15 L/min, with the order of effectiveness from high to low being aeration rate > C/N > moisture. This information could be used as a valuable reference for the in situ NH₃ emission control during kitchen waste composting.

     

Novel degradation pathway of 4-chloro-2-aminophenol via 4-chlorocatechol in Burkholderia sp. RKJ 800

Burkholderia sp. RKJ 800 utilized 4-chloro-2-aminophenol (4C2AP) as the sole carbon and energy source and degraded it with release of chloride and ammonium ions. The metabolic pathway of degradation of 4C2AP was studied and a novel intermediate, 4-chlorocatechol was identified as a major degradation product of 4C2AP using high-performance liquid chromatography and gas chromatography–mass spectrometry. Enzyme activities for 4C2AP-deaminase and 4-chlorocatechol-1,2-dioxygenase were detected in the crude extracts of the 4C2AP-induced cells of strain RKJ 800. The activity of the 4C2AP-deaminase confirmed the formation of 4-chlorocatechol from 4C2AP and the 4-chlorocatechol-1,2-dioxygenase activity suggested the cleavage of 4-chlorocatechol into 3-chloro-cis,cis-muconate. On the basis of the identified metabolites, we have proposed a novel degradation pathway of 4C2AP for Burkholderia sp. RKJ 800. Furthermore, the potential of Burkholderia sp. RKJ 800 to degrade 4C2AP in soil was also investigated using microcosm studies under laboratory conditions. The results of microcosm studies conclude that Burkholderia sp. RKJ 800 was able to degrade 4C2AP in soil and may be used to remediate 4C2AP-contaminated site. This is the first report of (1) the formation of 4-chlorocatechol and 3-chloro-cis,cis-muconate in the degradation pathway of 4C2AP and (2) bioremediation of 4C2AP by any bacterium.     

Using variances in hydrocarbon concentration and carbon stable isotope to determine the important influence of irrigated water on petroleum accumulation in surface soil

Hunpu is a wastewater-irrigated area southwest of Shenyang. To evaluate petroleum contamination and identify its sources at the area, the aliphatic hydrocarbons and compound-specific carbon stable isotopes of n-alkanes in the soil, irrigation water, and atmospheric deposition were analyzed. The analyses of hydrocarbon concentrations and geochemical characteristics reveal that the water is moderately contaminated by degraded heavy oil. According to the isotope analysis, inputs of modern C3 plants and degraded petroleum are present in the water, air, and soil. The similarities and dissimilarities among the water, air, and soil samples were determined by concentration, isotope, and multivariate statistical analyses. Hydrocarbons from various sources, as well as the water/atmospheric deposition samples, are more effectively differentiated through principal component analysis of carbon stable isotope ratios (δ¹³C) relative to hydrocarbon concentrations. Redundancy analysis indicates that 57.1 % of the variance in the δ¹³C of the soil can be explained by the δ¹³C of both the water and air, and 35.5 % of the variance in the hydrocarbon concentrations of the soil can be explained by hydrocarbon concentrations of both the water and the air. The δ¹³C in the atmospheric deposition accounts for 28.2 % of the δ¹³C variance in the soil, which is considerably higher than the variance in hydrocarbon concentrations of the soil explained by hydrocarbon concentrations of the atmospheric deposition (7.7 %). In contrast to δ¹³C analysis, the analysis of hydrocarbon concentrations underestimates the effect of petroleum contamination in the irrigated water and air on the surface soil. Overall, the irrigated water exerts a larger effect on the surface soil than does the atmospheric deposition.     

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.