Showing papers on "Oxalic acid published in 2011"

In-cloud oxalate formation in the global troposphere: a 3-D modeling study

Abstract: . Organic acids attract increasing attention as contributors to atmospheric acidity, secondary organic aerosol mass and aerosol hygroscopicity. Oxalic acid is globally the most abundant dicarboxylic acid, formed via chemical oxidation of gas-phase precursors in the aqueous phase of aerosols and droplets. Its lifecycle and atmospheric global distribution remain highly uncertain and are the focus of this study. The first global spatial and temporal distribution of oxalate, simulated using a state-of-the-art aqueous-phase chemical scheme embedded within the global 3-dimensional chemistry/transport model TM4-ECPL, is here presented. The model accounts for comprehensive gas-phase chemistry and its coupling with major aerosol constituents (including secondary organic aerosol). Model results are consistent with ambient observations of oxalate at rural and remote locations (slope = 1.16 ± 0.14, r2 = 0.36, N = 114) and suggest that aqueous-phase chemistry contributes significantly to the global atmospheric burden of secondary organic aerosol. In TM4-ECPL most oxalate is formed in-cloud and less than 5 % is produced in aerosol water. About 62 % of the oxalate is removed via wet deposition, 30 % by in-cloud reaction with hydroxyl radical, 4 % by in-cloud reaction with nitrate radical and 4 % by dry deposition. The in-cloud global oxalate net chemical production is calculated to be about 21–37 Tg yr−1 with almost 79 % originating from biogenic hydrocarbons, mainly isoprene. This condensed phase net source of oxalate in conjunction with a global mean turnover time against deposition of about 5 days, maintain oxalate's global tropospheric burden of 0.2–0.3 Tg, i.e. 0.05–0.1 Tg-C that is about 5–9 % of model-calculated water soluble organic carbon burden.

Influence of arbuscular mycorrhiza on organic solutes in maize leaves under salt stress

Abstract: A pot experiment was conducted to examine the effect of the arbuscular mycorrhizal (AM) fungus, Glomus mosseae, on plant biomass and organic solute accumulation in maize leaves. Maize plants were grown in sand and soil mixture with three NaCl levels (0, 0.5, and 1.0 g kg−1 dry substrate) for 55 days, after 15 days of establishment under non-saline conditions. At all salinity levels, mycorrhizal plants had higher biomass and higher accumulation of organic solutes in leaves, which were dominated by soluble sugars, reducing sugars, soluble protein, and organic acids in both mycorrhizal and non-mycorrhizal plants. The relative abundance of free amino acids and proline in total organic solutes was lower in mycorrhizal than in non-mycorrhizal plants, while that of reducing sugars was higher. In addition, the AM symbiosis raised the concentrations of soluble sugars, reducing sugars, soluble protein, total organic acids, oxalic acid, fumaric acid, acetic acid, malic acid, and citric acid and decreased the concentrations of total free amino acids, proline, formic acid, and succinic acid in maize leaves. In mycorrhizal plants, the dominant organic acid was oxalic acid, while in non-mycorrhizal plants, the dominant organic acid was succinic acid. All the results presented here indicate that the accumulation of organic solutes in leaves is a specific physiological response of maize plants to the AM symbiosis, which could mitigate the negative impact of soil salinity on plant productivity.

Enhanced Cationic Dyes Removal from Aqueous Solution by Oxalic Acid Modified Rice Husk

Abstract: The adsorption of two basic dyes, namely, methylene blue (MB) and malachite green (MG), onto natural rice husk (NRH) and oxalic acid modified rice husk (MRH) was studied in a batch adsorption system. Factors influencing dyes adsorption such as the concentration of the adsorbate, the pH, the salt concentration, the temperature, and the contact time were investigated. The Langmuir and Freundich isotherms were used to fit the equilibrium data, and the results showed that the Langmuir isotherm exhibited a little better fit to the MG adsorption data by both adsorbents, while the Freundlich isotherm seemed to agree better with the MB adsorption. The kinetic experimental data were analyzed using three kinetic equations, via the pseudo-first-order equation, the pseudo-second-order equation, and the intraparticle diffusion model, to examine the mechanism of adsorption and the potential rate-controlling step. The mechanism of the process was found to be complex, consisting of both surface adsorption and pore diffus...

Ozonation of model organic compounds catalysed by nanostructured cerium oxides

Abstract: Cerium oxides prepared by the precipitation method and hydrothermal synthesis, with distinct morphologies and particle size, were tested as catalysts in the ozonation of selected organic compounds. Oxalic acid, aniline and a reactive dye were used as representative of organic pollutants. In the case of oxalic acid, an increase in the catalytic activity with the increase of the percentage of Ce(III) on the surface was observed. Both single and catalytic ozonation allowed the total removal of aniline after 30 min of reaction; the cerium oxide prepared by the precipitation method was the best catalyst for promoting the mineralization of aniline solutions. TOC removals close to 100% were obtained in all cases when cerium oxides were used as catalysts in the ozonation of the reactive dye tested.

Effect of Carboxylic Acid on Sintering of Inkjet-Printed Copper Nanoparticulate Films

Abstract: The reduction effect of various carboxylic acids on inkjet-printed copper film was investigated. Carboxylic acids were exposed to the film by nitrogen gas that was bubbled through the liquid acids during the annealing process. It was observed that in the case of saturated monocarboxylic acid (formic, acetic, propionic, butyric), the acids with shorter hydrocarbon chains perform better in reducing the surface copper oxides in the printed copper conductive film. The printed films exposed to formic acid vapor exhibited the lowest resistivity (3.10 and 2.30 μΩ cm when annealed at 200 and 250 °C, respectively). In addition, the oxalic acid more effectively reduces copper oxide than formic acid and its usage can shorten the annealing time for highly conductive printed copper film. This reductive annealing process allows fabrication of copper patterns with low resistivity, (3.82 μΩ cm annealed at 250 °C) comparable to the resistivity of bulk copper.

Photocatalytic reduction of nitrobenzenes to aminobenzenes in aqueous suspensions of titanium(IV) oxide in the presence of hole scavengers under deaerated and aerated conditions

Abstract: Photocatalytic reduction of nitrobenzenes to corresponding aminobenzenes in aqueous suspensions of titanium(IV) oxide (TiO2) containing hole scavengers under various conditions was examined. In photocatalytic reduction of m-nitrobenzenesulfonic acid (m-NBS) in the presence of formic acid (FA) under deaerated conditions, m-aminobenzenesulfonic acid (m-ABS) was produced almost quantitatively in acidic suspensions and high efficiency (>99%) in FA utilization as a hole scavenger was achieved. No re-oxidation of m-ABS occurred in acidic conditions both in the presence and absence of FA. The high yield of m-ABS was explained by strong ability of FA as a hole scavenger and possible repulsion of the reduced functional group (ammonium group, –NH3+) from the protonated, i.e., positively charged TiO2 surface in acidic suspensions avoiding re-oxidation of m-ABS. Using TiO2 samples of various physical properties, which had been synthesized by a solvothermal method and post-calcination at various temperatures, effects of physical properties of the TiO2 samples on m-ABS yield were also investigated. A linear correlation between the amount of m-NBS adsorbed and the m-ABS yield was observed, suggesting that ability of TiO2 for m-NBS adsorption is one of the key factors for effective photocatalytic reduction of m-NBS to m-ABS. This photocatalytic system can be applied for reduction of aminonitrobenzenes to corresponding diaminobenzenes (DAB) in the presence of oxalic acid as a hole scavenger. High yields of m-ABS and DAB were achieved even when the reactions were performed in the presence of oxygen.

Oxalate metal complexes in aerosol particles: implications for the hygroscopicity of oxalate-containing particles

Abstract: . Atmospheric aerosols have both a direct and an indirect cooling effect that influences the radiative balance at the Earth's surface. It has been estimated that the degree of cooling is large enough to weaken the warming effect of carbon dioxide. Among the cooling factors, secondary organic aerosols (SOA) play an important role in the solar radiation balance in the troposphere as SOA can act as cloud condensation nuclei (CCN) and extend the lifespan of clouds because of their high hygroscopic and water soluble nature. Oxalic acid is an important component of SOA, and is produced via several formation pathways in the atmosphere. However, it is not certain whether oxalic acid exists as free oxalic acid or as metal oxalate complexes in aerosols, although there is a marked difference in their solubility in water and their hygroscopicity. We employed X-ray absorption fine structure spectroscopy to characterize the calcium (Ca) and zinc (Zn) in aerosols collected at Tsukuba in Japan. Size-fractionated aerosol samples were collected for this purpose using an impactor aerosol sampler. It was shown that 10–60% and 20–100% of the total Ca and Zn in the finer particles (

Evidence of a natural marine source of oxalic acid and a possible link to glyoxal

Abstract: [1] This paper presents results supporting the existence of a natural source of oxalic acid over the oceans. Oxalate was detected in “clean-sector” marine aerosol samples at Mace Head (Ireland) (53°20′N, 9°54′W) during 2006, and at Amsterdam Island (37°48′S, 77°34′E) from 2003 to 2007, in concentrations ranging from 2.7 to 39 ng m−3 and from 0.31 to 17 ng m−3, respectively. The oxalate concentration showed a clear seasonal trend at both sites, with maxima in spring-summer and minima in fall-winter, being consistent with other marine biogenic aerosol components (e.g., methanesulfonic acid, non-sea-salt sulfate, and aliphatic amines). The observed oxalate was distributed along the whole aerosol size spectrum, with both a submicrometer and a supermicrometer mode, unlike the dominant submicrometer mode encountered in many polluted environments. Given its mass size distribution, the results suggest that over remote oceanic regions oxalate is produced through a combination of different formation processes. It is proposed that the cloud-mediated oxidation of gaseous glyoxal, recently detected over remote oceanic regions, may be an important source of submicrometer oxalate in the marine boundary layer. Supporting this hypothesis, satellite-retrieved glyoxal column concentrations over the two sampling sites exhibited the same seasonal concentration trend of oxalate. Furthermore, chemical box model simulations showed that the observed submicrometer oxalate concentrations were consistent with the in-cloud oxidation of typical marine air glyoxal mixing ratios, as retrieved by satellite measurements, at both sites.

Mercury removal from aqueous solutions of HgCl2 by heterogeneous photocatalysis with TiO2

Abstract: The photocatalytic removal of Hg(II) from aqueous solutions of HgCl 2 using TiO 2 as catalyst was studied. The influence of pH and the addition of methanol, formic acid and oxalic acid as sacrificial additives on the extent of Hg(II) adsorption and photocatalytic reduction was investigated. The results showed that the overall process strongly depended on pH, being enhanced as the pH was increased. At pH 10, an efficient removal of Hg(II) was achieved even in the absence of organic additives, attaining final mercury concentrations in solution at trace levels (μg L −1 ). In acidic conditions, the addition of sacrificial organic molecules significantly increased the rate and extent of aqueous Hg(II) removal. The nature and distribution of mercury products deposited on the catalyst was dependent on the reaction conditions. In the absence of additives, Hg 2 Cl 2 and Hg 0 were respectively identified in acidic and neutral/alkaline media as main reduced species on the titania surface. The addition of organic additives enhanced the photocatalytic reduction to Hg 0 . Comparison between adsorption and reaction results evidenced that it cannot be established a direct correlation between Hg(II) dark adsorption on the TiO 2 surface and the efficiency of Hg(II) photoreduction achieved.

Catalytic activity and stability of multiwalled carbon nanotubes in catalytic wet air oxidation of oxalic acid: The role of the basic nature induced by the surface chemistry

Abstract: Different chemical and thermal treatments (nitric acid at boiling temperature, liquid-phase urea treatment at 200 °C, and gas-phase thermal treatment with nitrogen at 600 °C) were applied to multiwalled carbon nanotubes (MWCNTs) in order to produce materials with different textural and chemical properties. Nitrogen adsorption isotherms, temperature programmed desorption, pH pzc (point of zero charge), elemental analysis and X-ray photoelectron spectroscopy were used to characterize these materials. The chemical and thermal treatments have influence on the materials pH pzc , which decreases upon nitric acid treatment and increases with urea or gas-phase thermal treatments. The original and modified MWCNTs, without any impregnated metal, were investigated as catalysts in the catalytic wet air oxidation (CWAO) process, using oxalic acid as model compound at 140 °C and 40 bar of total pressure. Oxalic acid is very stable under non-catalytic conditions but can be totally degraded in less than 30 min in the presence of MWCNTs. The rate of oxidation of oxalic acid depends on the chemical properties of MWCNTs, the apparent initial first-order rate constants being lower for the MWCNTs with a marked acid character. The textural properties of MWCNTs are stable in cyclic CWAO experiments, but a decrease of their basic character leads to the reduction of their catalytic activity, even if this activity is still high with reused catalysts (nearly total oxalic acid degradation in 45 min and complete mineralization in 120 min). Therefore, MWCNTs without any impregnated metal, especially those of more basic character, are very active catalysts for CWAO, their activity strongly depending on the stability of their surface chemistry.

Photocatalytic reduction of CO2 over Cu-TiO2 /molecular sieve 5A composite.

Abstract: TiO(2) and different Cu wt% loaded TiO(2) (TC(0.5-5.0)), 10 wt% TC(2.0) supported on molecular sieve 5A (10 wt% TC(2.0)/MS) were prepared by impregnation and solid-state dispersion methods. The photocatalysts prepared were characterized using XRD, SEM, and UV-Vis DRS, TEM, XPS spectroscopy techniques. Photocatalytic reduction of CO(2) in water and alkaline solution are investigated in a batch reactor. The yield of oxalic acid increased notably when TC was supported on molecular sieve. The Cu-TiO(2) supported on molecular sieve catalyst promotes the charge separation that leads to an increase in the selective formation of oxalic acid in addition to methanol, acetic acid and traces of methane. The product formation is due to the high adsorption of CO(2), water and product shape selectivity of the composite photocatalyst. The maximum yield of oxalic acid was found to be 65.6 μg h(-1) g(-1) per cat using 0.2 N NaOH containing solution over 10 wt% TC(2.0)/MS photocatalyst. The difference in the photocatalytic activity is related to its physicochemical properties.

LC–MS analysis of low molecular weight organic acids derived from root exudation

Abstract: A sensitive method for quantification of citric, fumaric, malic, malonic, oxalic, trans aconitic, and succinic acid in soil- and root-related samples is presented. The method is based on a novel, fast, and simple esterification procedure and subsequent analysis via liquid chromatography–mass spectrometry. Derivatization comprises in situ generation of HCl, which catalyzes the Fischer esterification with benzyl alcohol. As a key advance, the esterification with the aromate allows reversed-phase separation and improves electrospray ionization efficiency. The method provided procedural detection limits of 1 nM for citric, 47 nM for fumaric, 10 nM for malic, 10 nM for malonic, 16 nM for oxalic, 15 nM for succinic, and 2 nM for aconitic acid utilizing 500 μL of liquid sample. The working range was 3 nM to 10 μM for citric acid, 158 nM to 10 μM for fumaric acid, 34 nM to 10 μM for malic acid, 33 nM to 10 μM for malonic acid, 53 nM to 10 μM for oxalic acid, 48 nM to 10 μM for succinic acid, and 6 nM to 10 μM for aconitic acid. Quantification of the analytes in soil-related samples was performed via external calibration of the entire procedure utilizing 13C-labeled oxalic and citric acid as internal standards. The robustness of the method was tested with soil extracts and samples from hydroponic experiments. The latter concerned the regulation of phosphorus solubilization via plant root exudation of citric, malic, and oxalic acid.

Catalytic ozonation of organic pollutants in the presence of cerium oxide–carbon composites

Abstract: Cerium oxide–carbon composites were prepared and tested as ozonation catalysts for the removal of two selected carboxylic acids, oxalic and oxamic, and one textile dye (C.I. Reactive Blue 5). The results were compared with those obtained in non-catalytic ozonation and ozonation catalysed by cerium oxide and carbon materials (activated carbon, carbon xerogel). With the exception of cerium oxide, a total degradation of oxalic acid was obtained in approximately 90 min for all prepared catalysts and the catalytic activity increases with the amount of carbon present in the composites. Despite of oxamic acid be more refractory to ozonation than oxalic acid, 75% of oxamic acid removal was achieved after 10 h of reaction in the presence of the ceria-activated carbon composite with 90% of carbon material. In the mineralization of the textile dye, the catalytic activity of the composites increases with the amount of activated carbon introduced.

Highly stable Fe/γ‐Al2O3 catalyst for catalytic wet peroxide oxidation

Abstract: BACKGROUND: A highly stable Fe/γ-Al2O3 catalyst for catalytic wet peroxide oxidation has been studied using phenol as target pollutant. The catalyst was prepared by incipient wetness impregnation of γ-Al2O3 with an aqueous solution of Fe(NO3)3· 9H2O. The influence of pH, temperature, catalyst and H2O2 doses, as well as the initial phenol concentration has been analyzed. RESULTS: The reaction temperature and initial pH significantly affect both phenol conversion and total organic carbon removal. Working at 50 °C, an initial pH of 3, 100 mg L−1 of phenol, a dose of H2O2 corresponding to the stoichiometric amount and 1250 mg L−1 of catalyst, complete phenol conversion and a total organic carbon removal efficiency close to 80% were achieved. When the initial phenol concentration was increased to 1500 mg L−1, a decreased efficiency in total organic carbon removal was observed with increased leaching of iron that can be related to a higher concentration of oxalic acid, as by-product from catalytic wet peroxide oxidation of phenol. CONCLUSION: A laboratory synthesized γ-Al2O3 supported Fe has shown potential application in catalytic wet peroxide oxidation of phenolic wastewaters. The catalyst showed remarkable stability in long-term continuous experiments with limited Fe leaching, < 3% of the initial loading. Copyright © 2010 Society of Chemical Industry