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Sorption of zinc ions from aqueous solutions on regenerated activated carbons.

This paper discusses the increasing use of activated carbons to remove wastewater contaminants and their contribution to producing wastes abundant in heavy metals. Considering their threat to the environment and their possible recovery, research on the regeneration of spent carbon sorbents and catalysts is advisable. It has also been shown that it is possible to recover activated carbon from spent catalyst (CC(spent)) generated by vinyl acetate synthesis by using supercritical extraction with carbon dioxide or by leaching with hydrochloric acid or a solution of nitric acid assisted by microwave energy. Activated carbon recovered in this work had a high sorption for zinc ions that was comparable to that of fresh commercial activated carbon.

Adsorption↗

Thallium in soils and stream sediments of a Zn-Pb mining and smelting area.

Thallium was determined in 120 samples of soil and 30 samples of stream sediments from the southeastern part of the Silesian-Cracowian zinc-lead ore deposits. Soil samples were taken from topsoils (0.0-0.2 m) and bottom soils (0.8 and 1.0 m). Thallium was determined by flow-injection-differential-pulse anodic stripping voltammetry. The samples were decomposed sequentially with 73% hydrofluoric acid and a mixture of nitric acid and hydrogen peroxide. The results showed that zinc-lead ore mining as well as their processing and smelting leads to a significant increase of thallium in the top layer of soil and in stream sediments. The highest recorded concentration was 150 ppm Tl for stream sediment and 35 ppm for a soil sample. Thallium concentration in small rivers from the investigated area was by 2 orders of magnitude higher than in the reference area. The highest recorded concentration being 3.24 microg L(-1).

Environmental Monitoring↗

Anthocyanin and flavonoid production from Perilla frutescens: pilot plant scale processing including cross-flow microfiltration and reverse osmosis.

Extraction and concentration at a pilot plant scale of anthocyanins and flavonoids from Perilla frutescens var. frutescens harvested in the Guangzhou area of China were investigated. The study of extraction efficiency using mineral acids and organic acids showed that 0.01 mol/L nitric acid was the most suitable to extract flavonoids from this slightly red leaf cultivar. The red extract contained 12 mg/L (as cyanidin equivalent) anthocyanins and other flavones. The multistep process included cross-flow microfiltration (CFM) with a ceramic type membrane, reverse osmosis (RO), and rotating evaporation (RE). The filtration fluxes were high and constant for CFM (150 L/h/m2 at 0.6 b) and for RO (22 L/h/m2 at 40 b). The red extract was concentrated 9.4 times by RO and then 5.4 times by RE. It contained 422 mg/L anthocyanins, representing 77% of the total extracted anthocyanin. The proportion of flavonoids was found unchanged during processing. The concentrated extract showed a pH of 2.7, and its free acidity was found to be 46% of the acidity added for extraction, because of the buffering capacity of the extract. At the concentration level reached, a crystallized deposit occurred and was identified as tartrate.

Anthocyanins↗

Unprecedented selective ipso-nitration of calixarenes monitored by the O-substituents.

The electrophilic ipso-reactions of a tBu-calix[6]arene that presents alternate O-methyl and O-2-methylen-N-methyl-imidazolyl groups (1) at the small rim have been studied. Whereas 1 underwent per-sulfonation in sulfuric acid, it selectively reacted with nitric acid to yield a tris-nitro derivative. The ipso-nitration occurred regioselectively on the calixarene anisol units. The reaction has been studied with various tBu-calixarenes (2-11) presenting alternate anisol and phenol ether units. The regioselectivity of the process appeared to be correlated to the presence of a protonable site on the O-substituent. It is proposed that the corresponding protonated heteroatom (N for the amines, O for the amides and the carboxylic acid), situated in the gamma or epsilon position of the phenoxy moieties, deactivates the corresponding aromatic ring by removing electron density through intramolecular hydrogen bonding. The high control operated by the O-substituents at the small rim even allowed the selective ipso-nitration of partially detertiobutylated calixarene 1(H3). Hence, these findings open new routes to a wide range of nonsymmetrically substituted calixarenes at the large rim.

Journal Article↗

A nitro-hunsdiecker reaction: from unsaturated carboxylic acids to nitrostyrenes and nitroarenes.

[reaction: see text] The nitrodecarboxylation of aromatic alpha,beta-unsaturated carboxylic acids and ring-activated benzoic acids can be achieved using nitric acid (3 equiv) and catalytic AIBN (2 mol %) in MeCN. From the effect of various additives, the nitrodecarboxylation is postulated to involve the generation of an acyloxy radical RCO(2)(*) by a NO(3)(*) radical followed by attack of a NO(2)(*) radical.

Journal Article↗

Transport and fate of gaseous pollutants associated with the National Energy Program.

The experimental evidence related to the long-range transport and transformations of sulfates has been critically reviewed. It has been concluded that sulfate emissions from various sources can be superimposed on each other during long-range transport to create episodes far from the contributing sources. Sulfates are important contributors to degrading visibility through the United States including relatively pristine areas in the western United States. Acid sulfate components, along with nitric acid, may increase the problem of acidity in precipitation on soils, vegetation, and lakes in certain areas of the eastern United States. Improvements in monitoring of these pollutants are required to follow changes in air quality caused by long-range transport.

Air Pollutants↗

Biological nitrogen removal from industrial wastewater discharged from metal recovery processes.

The wastewater generated from the processes of recovering precious metals from industrial wastes contains high concentrations of acids and alkalis such as nitric acid and aqueous ammonia, and of salts such as sodium chloride and sodium sulfate. Biological nitrogen removal from this wastewater was attempted by using a circulating bioreactor system equipped with an anaerobic packed bed and an aerobic three-phase fluidized bed. As a result of acclimating microorganisms with change of the hydraulic residence time, this system effectively removed nitrogen from diluted wastewater (T-N: from 2,000 to 4,000 g/m3), such that the total nitrogen concentration in the effluent met the sewage discharge control criteria in Japan (240 g/m3). The removal ratio of total nitrogen was 90% to 98% and that of ammonia was 80% to 92%. In addition, the characteristic equations for biological treatment were applied to this system on the assumption that both reactions of denitrification in the anaerobic reactor and nitrification in the aerobic reactor can be approximated to a first-order reaction. This simplified approach successfully led to a new analytical method for simulating the optimum volume ratio of anaerobic reactor to aerobic reactor for minimizing the total hydraulic residence time.

Ammonia↗

Microhardness and scanning electron microscopy analysis of Nd:YAG laser and acid treatment effects in dentin.

Laser irradiation at and above parameters producing the modification threshold for dentin causes structural changes to the dentin surface. This study determined the microhardness of dentin before and after laser modification and acid treatment using a repeated-measures design. Seven dentin sections (4 mm in thickness) were cut from freshly extracted non-carious third molars using a diamond saw. The middle occlusal third was used as the test dentin surface. One section served as a control (C); three received laser modification (L) and then acid treatment (L + A); and three received acid (A) and then laser treatment (A + L). Laser modification was made using a pulsed (120 microseconds) fiber-optic-delivered (500 microns diameter) Nd:YAG (lambda = 1.06 microns) laser at the physical modification threshold of 207 J/cm2. Acid treatment consisted of 10% nitric acid applied for 45 seconds. Twenty Knoop indentation microhardness measurements (KHN) were obtained using 300 g force engaged for 15 seconds for each section before and after each treatment (n = 400). Knoop microhardness values recorded: C = 62 +/- 3; L = 149 +/- 35; A = 24 +/- 5; L + A = 40 +/- 16; and A + L = 33 +/- 5. Multifactor-repeated measures, with analysis of variance (ANOVA; p < or = 0.05), indicated significant differences between all treatment groups. Scanning electron microscopy analysis of dentin surfaces documented unique surface morphology for all treatment conditions. Laser modification of dentin before or after acid treatment increased dentin microhardness.

Adult↗

The effect of tissue decalcification on mRNA retention within bone for in-situ hybridization studies.

Tissue decalcification is a routine part of the preparation of bone tissue for histological studies. Although in-situ hybridization has been employed to localize mRNA of collagenous and non-collagenous bone related proteins in skeletal tissue, little is known regarding the effects of decalcifying agents on mRNA retention within tissue. In this study in-situ hybridization using an oligonucleotide probe (i.e. a poly d(T) probe) to detect total messenger RNA has been employed to investigate the effects of the decalcifying agents nitric acid, formic acid and EDTA on mRNA retention compared to undeacalcified tissue. The results show that formalin fixation and EDTA decalcification preserve substantial amounts of mRNA within the tissue. In particular, this study illustrates that it is possible to perform in-situ hybridization on formalin fixed decalcified paraffin embedded tissue.

Bone and Bones↗

Removal of dyes from aqueous solution using fly ash and red mud.

Fly ash and red mud have been employed as adsorbents for the removal of a typical basic dye, methylene blue, from aqueous solution. Heat treatment and chemical treatment have also been applied to the as-received fly ash and red mud samples. It is found that fly ash generally shows higher adsorption capacity than red mud. The raw fly ash and red mud show adsorption capacity at 1.4 x 10(-5) and 7.8 x 10(-6) mol/g, respectively. Heat treatment reduces the adsorption capacity for both fly ash and red mud but acid treatment by HNO(3) induces a different effect on fly ash and red mud. Nitric acid treatment results in an increase in adsorption capacity of fly ash (2.4 x 10(-5) mol/g) while it decreases the adsorption capacity for red mud (3.2 x 10(-6) mol/g). The adsorption data have been analysed using Langmuir, Freundlich and Redlich-Peterson isotherms. The results indicate that the Redlich-Peterson model provides the best correlation of the experimental data. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption. For fly ash and red mud, adsorption of methylene blue is endothermic reaction with DeltaH(0) at 76.1 and 10.8 kJ/mol, respectively.

Adsorption↗

Atomic force microscopy of acid effects on dentin.

Atomic force microscopy (AFM) was used in the examination of the early stages of acid treatment of dentin. Disks of highly polished dentin were initially examined under deionized water and following exposure to 0.025 M nitric acid for 20 s intervals from 0-100 s. Peritubular depth changes were linear (0.005 microns/s). The intertubular dentin surface initially moved at approximately 1/2 the peritubular rate and then reached a plateau as the demineralized collagen scaffold collapsed. There was no apparent difference in the tubule center-to-center distance during the treatment. Differences in the movement and morphology of the zones are of importance in dentin bonding applications relying on penetration of the demineralized dentin by adhesive monomers. The changes are probably related to the partial collapse of the collagen matrix. Alternatively, access to the apatite crystals and solubility may be higher in the peritubular zone. AFM appears to hold exceptional promise for the study of conditioning and priming agents for dentin bonding.

Acid Etching, Dental↗

The effects of sequential exposure to acidic fog and ozone on pulmonary function in exercising subjects.

In Southern California coastal regions, morning fog is often acidified by the presence of nitric acid (HNO3). Peak exposure to ozone (O3) usually occurs in the afternoon and evening, after the fog has dissipated. To determine whether fog containing HNO3 might enhance pulmonary responses to O3, we studied a group of healthy, athletic subjects selected for lung function sensitivity to O3. On 3 separate days, the subjects exercised for 2 h in atmospheres containing HNO3 fog (0.5 mg/ml), H2O fog, or clean, filtered air. After a 1-h break, they exercised for an additional 3 h in an atmosphere containing 0.20 ppm O3. Surprisingly, the mean O3-induced decrements in FEV1 and FVC were smaller after exercise in each fog-containing atmosphere than they were after exercise in clean, filtered air. The mean (+/- SEM) O3-induced decrements in FEV1 were 26.4 +/- 5.3% after air, 17.1 +/- 3.7% after H2O fog, and 18.0 +/- 4.3% after HNO3 fog, and in FVC they were 19.9 +/- 4.7% after air, 13.6 +/- 2.8% after H2O fog, and 13.6 +/- 4.2% after HNO3 fog.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗

Effect of passivation and surface modification on the dissolution behavior and nano-surface characteristics of Ti-6Al-4V in Hank/EDTA solution.

The aim of the present study was to investigate the effects of passivation treatment (34% nitric acid passivation, 400 ( composite function)C heated in air, and aged in 100 ( composite function)C de-ionized water) and surface modification (2 hr and 8 hr vacuum-brazed treatments) on the ion dissolution and nano-surface characteristics of Ti-6Al-4V exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid (EDTA) at 37 ( composite function)C. The results indicated that the original nano-surface characteristics and microstructure would influence the ion dissolution but not change the capability of the Ca and P adsorption upon immersion. Of the three passivated treatments, 400 ( composite function)C thermal treatment for both 2 hr brazed Ti-6Al-4V (B2) and 8 hr brazed Ti-6Al-4V (B8) exhibits a substantial reduction in the constituent release compared to the acid passivated and water aged treatment, because the thicker thickness and rutile structure of surface oxide could provide the better dissolution resistance for 400 ( composite function)C-treated specimens. Moreover, the reduced Ti(2)Cu and increased alpha -titanium structure in B8 specimen could also improve ion dissolution resistance in comparison with B2 specimen. After soaking in Hank/EDTA solution, the adsorbed non-elemental Ca and P for all groups of specimens were observed by XPS analysis, and the AES depth-profile analysis indicate that the oxide films of all groups of specimens thicken with the longer immersion periods. The increasing oxide thickness may be the factor in the improved dissolution resistance at the longer immersion periods. The relation between lower dissolution rate and thicker oxide films were observed for all groups of specimens. The results suggest that the dissolution kinetics was governed by the metal ion transport through the oxide film in this study.

Air↗

Considerations of acidifying water samples for 99Tc analysis.

Environmental water samples are routinely acidified before radionuclide analysis to prevent adsorption of radionuclides on the container walls. This study addresses the concern for volatilizing 99Tc from acid solutions during evaporation before beta analysis has been addressed. Water samples can be acidified to pH 1.7 with nitric acid and evaporated to dryness on planchets without significant losses of technetium due to volatilization. However, the planchets should not be flamed unless a detergent is used, and control samples should be flamed to determine the loss of activity under the conditions used.

Environmental Pollutants↗

Removal of methyl parathion from water by electrochemically generated Fenton's reagent.

The electro-Fenton process was used to assess the degradation of methyl parathion (MP) in aqueous solutions. This oxidation process allows the production of hydroxyls radicals which react on the organic compounds, leading to their mineralization. Degradation experiments were performed either in perchloric, sulphuric, hydrochloric and nitric acid media under current controlled electrolysis conditions at different pH. The pH effect as well as the nature of the medium (i.e., the nature of the ions present in medium) on the degradation and mineralization efficiency were studied. The mineralization of the initial pollutant was investigated by total organic carbon measurements which show a complete mineralization at pH 3 in perchloric medium. The absolute rate constant of MP hydroxylation reaction was determined as (4.20+/-0.11)x10(9)M(-1)s(-1). Complete degradation of MP and its metabolites occur in less than 45min. Degradation reaction intermediates such as aromatic compounds, carboxylic acids and inorganic ions were identified and a mineralization pathway is proposed.

Carbon↗

Rapid digestion and flameless atomic absorption spectroscopy of mercury in fish: collaborative study.

A collaborative study of the determination of mercury in fish has been completed in which wet oxidation of fish tissue in nitric acid, using vanadium as a catalyst, is compared with the AOAC official final action digestion technique, 25.103-25.105, involving a nitric-perchloric acid mixture. The study used tuna fish samples of known mercury content and included spike recovery studies in which methyl mercury solutions of known composition were provided to each laboratory. The study was designed to provide recovery information that bracketed the regulatory level of mercury in fish. The results indicate that the proposed digestion method is at least as precise and accurate as the AOAC method. The proposed method is also more rapid and less hazardous. It has been adopted as official first action.

Animals↗

Potential risks to human respiratory health from "acid fog": evidence from experimental studies of volunteers.

Observations of high acidity (pH as low as 1.7) in fogwater collected in polluted areas have provoked concern for public health. Effects of exposure to acidic pollutants have not been studied under foggy conditions; thus there is no directly relevant information from which to estimate the health risk. Indirectly relevant information is available from numerous studies of volunteers exposed to "acid fog precursors" under controlled conditions at less than 100% relative humidity. The effect of fog in modifying responses to inhaled acidic pollutants is difficult to predict: depending on circumstances, fog droplets might either increase or decrease the effective dose of pollutants to the lower respiratory tract. Fog inhalation per se may have unfavorable effects in some individuals. Sulfur dioxide is known to exacerbate airway constriction in exercising asthmatics, at exposure concentrations attainable in ambient air. Nitrogen dioxide has shown little untoward respiratory effect at ambient concentrations in most studies, although it has been suggested to increase bronchial reactivity. Sulfuric acid aerosol has shown no clear effects at concentrations within the ambient range. At somewhat higher levels, increased bronchial reactivity and change in mucociliary clearance have been suggested. Almost no information is available concerning nitric acid.

Acids↗

On the adsorption/oxidation of hydrogen sulfide on activated carbons at ambient temperatures.

Activated carbons of various origins (bituminous coal, wood, coconut shells, and peat) were studied as adsorbents of hydrogen sulfide. Before the experiments the surface of the adsorbents was characterized by using the sorption of nitrogen, Boehm and potentiometric titrations, thermal analysis, and FTIR. The adsorbents were chosen to differ in their surface areas, pore volumes, and surface acidities. To broaden the spectrum of surface acidity, carbons were oxidized by using nitric acid and ammonium persulfate. After hydrogen sulfide adsorption the species present on the surface were analyzed using thermal analysis, ion chromatography, and elemental analysis. The H(2)S breakthrough capacity tests showed that the performances of different carbons differ significantly. For a good performance of carbons as hydrogen sulfide adsorbents a proper combination of surface chemistry of carbon and porosity is needed. It was demonstrated that a more acidic environment promotes the formation of sulfur oxides and sulfuric acid despite yielding small H(2)S removal capacities. On the other hand, a basic environment favors the formation of elemental sulfur (sulfur radicals) and yields high capacities. The presence of a sufficient amount of water preadsorbed on the carbon surface to facilitate dissociation also plays an important role in the process of H(2)S adsorption/oxidation. The results showed that there is a critical value in carbon surface acidity, which when exceeded results in a negligible hydrogen sulfide breakthrough capacity. This is consistent with the mechanism of H(2)S adsorption on unmodified carbons, where the rate-limiting step is the reaction of adsorbed hydrogen sulfide ion with dissociatively adsorbed oxygen. When the acidity is expressed as pH, its value should be higher than 5 to ensure the effective removal of hydrogen sulfide from the gas phase. Study of carbon regeneration using water washing and heat treatment showed that the adsorbents can be regenerated to about 40% of their initial capacity.

Journal Article↗